High strength polyurethane foam compositions and methods

ABSTRACT

Disclosed are high strength polyurethane foam compositions and methods of making them. In one aspect, the inventive polyurethane foams include strength enhancing additives comprising one or more polycarbonate polyols derived from the copolymerization of CO 2  and one or more epoxides. In one aspect, the inventive methods include the step of substituting a portion of the polyether polyol in the B-side of a foam formulation with one or more polycarbonate polyols derived from the copolymerization of CO 2  and one or more epoxides.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/368,110, filed Dec. 2, 2016 (now U.S. Pat. No. 10,047,188),which is a continuation of U.S. patent application Ser. No. 14/440,903,filed May 6, 2015 (now U.S. Pat. No. 9,512,259), which is a nationalphase application under 35 U.S.C. § 371 of PCT International ApplicationNo. PCT/US2013/068932, filed Nov. 7, 2013, which claims priority to U.S.Provisional Patent Application Ser. No. 61/758,500, filed Jan. 30, 2013,61/731,723, filed Nov. 30, 2012, and 61/723,627, filed Nov. 7, 2012, theentire contents each of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention pertains to the field of polyurethane foams. Moreparticularly, the invention pertains to additives and methods forincreasing the strength of polyurethane foams.

BACKGROUND OF THE INVENTION

Polyurethane foams derived from the reaction between polyisocyanates andreactive polymers are widely used in applications ranging frominsulation and manufacture of furniture, mattresses, consumer goods,construction materials, automotive components and the like.

The cost of polyurethane foams has increased dramatically in recentyears due to increases in the cost of petroleum-based feedstocks and theenergy used to make them. At the same time, the market demands areincreasing for high performing materials that are tough, have longservice lifetimes and improved sustainability profiles. Unfortunately,the current solutions to these problems tend to increase one property atthe expense of others.

For example, to make stronger foams, the density of the foam istypically increased leading to a greater use of materials and wastedenergy required to transport materials. This is exacerbated intransportation applications where the foam will be part of a vehiclesince the heavier foam will take a financial and environmental tollthrough increased fuel usage throughout its service lifetime. As such,compromises are often made wherein a less durable or lower performingfoam is selected based on cost or weight considerations.

Similarly, efforts to make foam compositions more sustainable byaddition of biobased feedstocks have had mixed results. Incorporation ofsoy or corn-based feedstocks in polyurethane foam formulations oftenleads to sacrifice of desirable properties and requires other changes tothe formulations to achieve acceptable performance-even with theseconcessions, it has been difficult to incorporate more than about 10% ofthe biobased material. The true sustainability of this approach is alsoquestionable especially when viewed as a whole, including the land andwater use and petroleum resources required to produce biobasedfeedstocks-particularly if additional effort or petroleum-basedadditives are required to compensate for negative effects thesematerials have on the foam formulations.

It has previously been reported that polyurethane foams can beformulated from polyols manufactured from CO₂ (see for example, co-ownedpatent applications WO 2010/028362 and PCT/US12/047967). These foamcompositions have improved carbon footprints since up to 50% of thepolyol's mass can be derived from waste CO₂ that would otherwise bereleased to the atmosphere. In addition to sequestering a potentialgreenhouse gas, this strategy allows the amount of fossil-fuel derivedfeedstock utilized in manufacturing the polyol to be cut by up to 50%.

Nonetheless, there remains a need for polyurethane foam compositionswith improved performance characteristics, and in particular forformulations that have superior strength and durability with equal orlesser weight than present materials.

SUMMARY OF THE INVENTION

As noted above, polyurethane foams incorporating epoxide CO₂ copolymers(aliphatic polycarbonate polyols) have been described. Nonetheless, incertain aspects these foams presented challenges. Foams formulated withepoxide CO₂ copolymers as the primary polyol component in the B-side canbe difficult to formulate (for example because of high viscosity).Furthermore, the foams produced are sometimes friable or lacking incertain other physical properties desirable in foams-especially inflexible foams. In one aspect, the present invention encompasses therecognition that when used as an additive in the B-side of a traditionalfoam formulation, the inclusion of epoxide CO₂ copolymers does not havethese negative effects, but instead their presence unexpectedlyincreases desirable properties such as strength, compression forcedeflection, solvent resistance and the like.

Therefore, in one aspect, the present invention encompasses highstrength polyurethane foam compositions comprising the reaction productof a polyol component and a polyisocyanate component, wherein the polyolcomponent comprises a blend of polyols including from about 2 weightpercent to about 50 weight of a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide. In certainembodiments, the remainder of the polyol component comprises traditionalpolyether or polyester polyols as are currently used in commercial foamformulations. The foam compositions of the present inventionunexpectedly demonstrate improved physical strength including highercompression force deflection and higher tear resistance than foamsformulated without the polycarbonate polyols. Importantly, theseimproved foam compositions do not have higher density than the initialfoam, and other factors pertaining to comfort, durability, insulationvalue and the like are not sacrificed.

In another aspect, the present invention encompasses methods ofstrengthening polyurethane foam compositions. In certain embodiments,the methods include a step of substituting from about 2 weight percentto about 50 weight percent of the polyol content of a polyurethane foamformulation with a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide.

In another aspect, the present invention provides strength enhancingadditives for foam formulations. The inventive additives comprisealiphatic polycarbonate polyols suitable for blending with polyether orpolyester polyols and characterized in that their presence in a foamformulation increases one or more of the compression force deflectionvalue, the tear resistance or the hysteresis of the final foamcomposition.

In another aspect, the present invention encompasses articles made fromhigh strength polyurethane foam compositions resulting from addingpolycarbonate polyols derived from the copolymerization of one or moreepoxides and carbon dioxide to the foam formulation. Such articlesinclude low density seating materials for transportation applications,non seating foam components for automobile manufacture, footwear foams,office furniture, mattresses, sporting goods, construction materials andconsumer goods.

DEFINITIONS

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein. Additionally, general principles of organicchemistry, as well as specific functional moieties and reactivity, aredescribed in Organic Chemistry, Thomas Sorrell, University ScienceBooks, Sausalito, 1999; Smith and March March's Advanced OrganicChemistry, 5^(th) Edition, John Wiley & Sons, Inc., New York, 2001;Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., NewYork, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^(rd)Edition, Cambridge University Press, Cambridge, 1987; the entirecontents of each of which are incorporated herein by reference.

Certain compounds of the present invention can comprise one or moreasymmetric centers, and thus can exist in various stereoisomeric forms,e.g., enantiomers and/or diastereomers. Thus, inventive compounds andcompositions thereof may be in the form of an individual enantiomer,diastereomer or geometric isomer, or may be in the form of a mixture ofstereoisomers. In certain embodiments, the compounds of the inventionare enantiopure compounds. In certain embodiments, mixtures ofenantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or moredouble bonds that can exist as either the Z or E isomer, unlessotherwise indicated. The invention additionally encompasses thecompounds as individual isomers substantially free of other isomers andalternatively, as mixtures of various isomers, e.g., racemic mixtures ofenantiomers. In addition to the above-mentioned compounds per se, thisinvention also encompasses compositions comprising one or morecompounds.

As used herein, the term “isomers” includes any and all geometricisomers and stereoisomers. For example, “isomers” include cis- andtrans-isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixturesthereof, as falling within the scope of the invention. For instance, astereoisomer may, in some embodiments, be provided substantially free ofone or more corresponding stereoisomers, and may also be referred to as“stereochemically enriched.”

Where a particular enantiomer is preferred, it may, in some embodimentsbe provided substantially free of the opposite enantiomer, and may alsobe referred to as “optically enriched.” “Optically enriched,” as usedherein, means that the compound or polymer is made up of a significantlygreater proportion of one enantiomer. In certain embodiments thecompound is made up of at least about 90% by weight of a preferredenantiomer. In other embodiments the compound is made up of at leastabout 95%, 98%, or 99% by weight of a preferred enantiomer. Preferredenantiomers may be isolated from racemic mixtures by any method known tothose skilled in the art, including chiral high pressure liquidchromatography (HPLC) and the formation and crystallization of chiralsalts or prepared by asymmetric syntheses. See, for example, Jacques, etal., Enantiomers, Racemates and Resolutions (Wiley Interscience, NewYork, 1981); Wilen, S. H., et al., Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, N Y, 1962); Wilen,S. H. Tables of Resolving Agents and Optical Resolutions p. 268 (E. L.Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, Ind. 1972).

The term “epoxide”, as used herein, refers to a substituted orunsubstituted oxirane. Such substituted oxiranes include monosubstitutedoxiranes, disubstituted oxiranes, trisubstituted oxiranes, andtetrasubstituted oxiranes. Such epoxides may be further optionallysubstituted as defined herein. In certain embodiments, epoxides comprisea single oxirane moiety. In certain embodiments, epoxides comprise twoor more oxirane moieties.

The term “polymer”, as used herein, refers to a molecule of highrelative molecular mass, the structure of which comprises the multiplerepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass. In certain embodiments, a polymer iscomprised of substantially alternating units derived from CO₂ and anepoxide (e.g., poly(ethylene carbonate). In certain embodiments, apolymer of the present invention is a copolymer, terpolymer,heteropolymer, block copolymer, or tapered heteropolymer incorporatingtwo or more different epoxide monomers. With respect to the structuraldepiction of such higher polymers, the convention of showing enchainmentof different monomer units separated by a slash may be used herein

These structures are to be interpreted to encompass copolymersincorporating any ratio of the different monomer units depicted unlessotherwise specified. This depiction is also meant to represent random,tapered, block copolymers, and combinations of any two or more of theseand all of these are implied unless otherwise specified.

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. Unless otherwisespecified, aliphatic groups contain 1-40 carbon atoms. In certainembodiments, aliphatic groups contain 1-20 carbon atoms. In certainembodiments, aliphatic groups contain 3-20 carbon atoms. In certainembodiments, aliphatic groups contain 1-12 carbon atoms. In certainembodiments, aliphatic groups contain 1-8 carbon atoms. In certainembodiments, aliphatic groups contain 1-6 carbon atoms. In someembodiments, aliphatic groups contain 1-5 carbon atoms, in someembodiments, aliphatic groups contain 1-4 carbon atoms, in someembodiments aliphatic groups contain 1-3 carbon atoms, and in someembodiments aliphatic groups contain 1 or 2 carbon atoms. Suitablealiphatic groups include, but are not limited to, linear or branched,alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, or phosphorus. In certain embodiments, one to six carbon atomsare independently replaced by one or more of oxygen, sulfur, nitrogen,or phosphorus. Heteroaliphatic groups may be substituted orunsubstituted, branched or unbranched, cyclic or acyclic, and includesaturated, unsaturated or partially unsaturated groups.

As used herein, the term “bivalent C₁₋₈ (or C₁₋₃) saturated orunsaturated, straight or branched, hydrocarbon chain”, refers tobivalent alkyl, alkenyl, and alkynyl, chains that are straight orbranched as defined herein.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic or polycyclic ring systems, asdescribed herein, having from 3 to 12 members, wherein the aliphaticring system is optionally substituted as defined above and describedherein. Cycloaliphatic groups include, without limitation, cyclopropyl,cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornmyl,adamantyl, and cyclooctadienyl. In some embodiments, the cycloalkyl has3-6 carbons. The terms “cycloaliphatic”, “carbocycle” or “carbocyclic”also include aliphatic rings that are fused to one or more aromatic ornonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl,where the radical or point of attachment is on the aliphatic ring. Incertain embodiments, the term “3- to 7-membered carbocycle” refers to a3- to 7-membered saturated or partially unsaturated monocycliccarbocyclic ring. In certain embodiments, the term “3- to 8-memberedcarbocycle” refers to a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocyclic ring. In certain embodiments, theterms “3- to 14-membered carbocycle” and “C₃₋₁₄ carbocycle” refer to a3- to 8-membered saturated or partially unsaturated monocycliccarbocyclic ring, or a 7- to 14-membered saturated or partiallyunsaturated polycyclic carbocyclic ring.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived from an aliphatic moietycontaining between one and six carbon atoms by removal of a singlehydrogen atom. Unless otherwise specified, alkyl groups contain 1-12carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbonatoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. Insome embodiments, alkyl groups contain 1-5 carbon atoms, in someembodiments, alkyl groups contain 1-4 carbon atoms, in some embodimentsalkyl groups contain 1-3 carbon atoms, and in some embodiments alkylgroups contain 1-2 carbon atoms. Examples of alkyl radicals include, butare not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl,iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl,neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl,dodecyl, and the like.

The term “alkenyl,” as used herein, denotes a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon double bond by the removal of a single hydrogen atom.Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. Incertain embodiments, alkenyl groups contain 2-8 carbon atoms. In certainembodiments, alkenyl groups contain 2-6 carbon atoms. In someembodiments, alkenyl groups contain 2-5 carbon atoms, in someembodiments, alkenyl groups contain 2-4 carbon atoms, in someembodiments alkenyl groups contain 2-3 carbon atoms, and in someembodiments alkenyl groups contain 2 carbon atoms. Alkenyl groupsinclude, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl,and the like.

The term “alkynyl,” as used herein, refers to a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon triple bond by the removal of a single hydrogen atom.Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. Incertain embodiments, alkynyl groups contain 2-8 carbon atoms. In certainembodiments, alkynyl groups contain 2-6 carbon atoms. In someembodiments, alkynyl groups contain 2-5 carbon atoms, in someembodiments, alkynyl groups contain 2-4 carbon atoms, in someembodiments alkynyl groups contain 2-3 carbon atoms, and in someembodiments alkynyl groups contain 2 carbon atoms. Representativealkynyl groups include, but are not limited to, ethynyl, 2-propynyl(propargyl), 1-propynyl, and the like.

The term “alkoxy”, as used herein refers to an alkyl group, aspreviously defined, attached to the parent molecule through an oxygenatom. Examples of alkoxy, include but are not limited to, methoxy,ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, andn-hexoxy.

The term “acyl”, as used herein, refers to a carbonyl-containingfunctionality, e.g., —C(═O)R′, wherein R′ is hydrogen or an optionallysubstituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroarylgroup, or is a substituted (e.g., with hydrogen or aliphatic,heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogencontaining functionality (e.g., forming a carboxylic acid, ester, oramide functionality). The term “acyloxy”, as used here, refers to anacyl group attached to the parent molecule through an oxygen atom.

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of five to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In certainembodiments of the present invention, “aryl” refers to an aromatic ringsystem which includes, but is not limited to, phenyl, biphenyl,naphthyl, anthracyl and the like, which may bear one or moresubstituents. Also included within the scope of the term “aryl”, as itis used herein, is a group in which an aromatic ring is fused to one ormore additional rings, such as benzofuranyl, indanyl, phthalimidyl,naphthimidyl, phenanthridinyl, or tetrahydronaphthyl, and the like. Incertain embodiments, the terms “6- to 10-membered aryl” and “C₆₋₁₀ aryl”refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 ring atoms;having 6, 10, or 14 π electrons shared in a cyclic array; and having, inaddition to carbon atoms, from one to five heteroatoms. The term“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes anyoxidized form of nitrogen or sulfur, and any quaternized form of a basicnitrogen. Heteroaryl groups include, without limitation, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Nonlimiting examples includeindolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl,indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl,cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- orbicyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted. In certain embodiments, the term “5- to 10-memberedheteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3heteroatoms independently selected from nitrogen, oxygen, or sulfur, oran 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur. In certainembodiments, the term “5- to 12-membered heteroaryl” refers to a 5- to6-membered heteroaryl ring having 1 to 3 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur, or an 8- to 12-memberedbicyclic heteroaryl ring having 1 to 4 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7-14-membered polycyclicheterocyclic moiety that is either saturated or partially unsaturated,and having, in addition to carbon atoms, one or more, preferably one tofour, heteroatoms, as defined above. When used in reference to a ringatom of a heterocycle, the term “nitrogen” includes a substitutednitrogen. As an example, in a saturated or partially unsaturated ringhaving 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, thenitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as inpyrrolidinyl), or +NR (as in N-substituted pyrrolidinyl). In someembodiments, the term “3- to 7-membered heterocyclic” refers to a 3- to7-membered saturated or partially unsaturated monocyclic heterocyclicring having 1 to 2 heteroatoms independently selected from nitrogen,oxygen, or sulfur. In some embodiments, the term “3- to 12-memberedheterocyclic” refers to a 3- to 8-membered saturated or partiallyunsaturated monocyclic heterocyclic ring having 1 to 2 heteroatomsindependently selected from nitrogen, oxygen, or sulfur, or a 7- to12-membered saturated or partially unsaturated polycyclic heterocyclicring having 1-3 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, withoutlimitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl,tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl,dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl,and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”,“heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and alsoinclude groups in which a heterocyclyl ring is fused to one or morearyl, heteroaryl, or cycloaliphatic rings, such as indolinyl,3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherethe radical or point of attachment is on the heterocyclyl ring. Aheterocyclyl group may be mono- or bicyclic. The term“heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

As described herein, compounds of the invention may contain “optionallysubstituted” moieties. In general, the term “substituted”, whetherpreceded by the term “optionally” or not, means that one or morehydrogens of the designated moiety are replaced with a suitablesubstituent. Unless otherwise indicated, an “optionally substituted”group may have a suitable substituent at each substitutable position ofthe group, and when more than one position in any given structure may besubstituted with more than one substituent selected from a specifiedgroup, the substituent may be either the same or different at everyposition. Combinations of substituents envisioned by this invention arepreferably those that result in the formation of stable or chemicallyfeasible compounds. The term “stable”, as used herein, refers tocompounds that are not substantially altered when subjected toconditions to allow for their production, detection, and, in certainembodiments, their recovery, purification, and use for one or more ofthe purposes disclosed herein.

Suitable monovalent substituents on a substitutable carbon atom of an“optionally substituted” group are independently halogen;—(CH₂)₀₋₄R^(∘); —(CH₂)₀₋₄OR^(∘); —O—(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄CH(OR^(∘))₂; —(CH₂)₀₋₄SR^(∘); —(CH₂)₀₋₄Ph, which may besubstituted with R^(∘); —(CH₂)₀₋₄O(CH₂)₀₋₁Ph which may be substitutedwith R^(∘); —CH═CHPh, which may be substituted with R^(∘); —NO₂; —CN;—N₃; —(CH₂)₀₋₄N(R^(∘))₂; —(CH₂)₀₋₄N(R^(∘))C(O)R^(∘); —N(R^(∘))C(S)R^(∘);—(CH₂)₀₋₄N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))C(S)NR^(∘) ₂;—(CH₂)₀₋₄N(R^(∘))C(O)OR^(∘); —N(R^(∘))N(R^(∘))C(O)R^(∘);—N(R^(∘))N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))N(R^(∘))C(O)OR^(∘);—(CH₂)₀₋₄C(O)R^(∘); —C(S)R^(∘); —(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₄C(O)SR; —(CH₂)₀₋₄C(O)OSiR^(∘) ₃;—(CH₂)₀₋₄OC(O)R^(∘); —OC(O)(CH₂)₀₋₄SR—, SC(S)SR^(∘);—(CH₂)₀₋₄SC(O)R^(∘); —(CH₂)₀₋₄C(O)NR^(∘) ₂; —C(S)NR^(∘) ₂; —C(S)SR^(∘);—SC(S)SR^(∘), —(CH₂)₀₋₄OC(O)NR^(∘) ₂; —C(O)N(OR)R^(∘); —C(O)C(O)R^(∘);—C(O)CH₂C(O)R^(∘); —C(NOR^(∘))R^(∘); —(CH₂)₀₋₄SSR^(∘);—(CH₂)₀₋₄S(O)₂R^(∘); —(CH₂)₀₋₄S(O)₂OR^(∘); —(CH₂)₀₋₄OS(O)₂R^(∘);—S(O)₂NR^(∘) ₂; —(CH₂)₀₋₄S(O)R^(∘); —N(R^(∘))S(O)₂NR^(∘) ₂;—N(R^(∘))S(O)₂R^(∘); —N(OR^(∘))R^(∘); —C(NH)NR^(∘) ₂; —P(O)₂R^(∘);—P(O)R^(∘) ₂; —OP(O)R^(∘) ₂; —OP(O)(OR^(∘))₂; SiR^(∘) ₃; —(C₁₋₄ straightor branched alkylene)O—N(R^(∘))₂; or —(C₁₋₄ straight or branchedalkylene)C(O)O—N(R^(∘))₂, wherein each R^(∘) may be substituted asdefined below and is independently hydrogen, C₁₋₈ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur, or, notwithstanding the definition above, twoindependent occurrences of R^(∘), taken together with their interveningatom(s), form a 3-12-membered saturated, partially unsaturated, or arylmono- or polycyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur, which may be substituted as definedbelow.

Suitable monovalent substituents on R^(∘) (or the ring formed by takingtwo independent occurrences of R^(∘) together with their interveningatoms), are independently halogen, —(CH₂)₀₋₂R^(●), -(haloR^(●)),—(CH₂)₀₋₂OH, —(CH₂)₀₋₂OR^(●), —(CH₂)₀₋₂CH(OR^(●))₂; —O(haloR^(●)), —CN,—N₃, —(CH₂)₀₋₂C(O)R^(●), —(CH₂)₀₋₂C(O)OH, —(CH₂)₀₋₂C(O)OR^(●),—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₂SR^(●), —(CH₂)₀₋₂SH, —(CH₂)₀₋₂NH₂,—(CH₂)₀₋₂NHR^(●), —(CH₂)₀₋₂NR^(●) ₂, —NO₂, —SiR^(●) ₃, —OSiR^(●) ₃,—C(O)SR^(●), —(C₁₋₄ straight or branched alkylene)C(O)OR^(●), or—SSR^(●) wherein each R^(●) is unsubstituted or where preceded by “halo”is substituted only with one or more halogens, and is independentlyselected from C₁₋₄ aliphatic, —CH₂Ph, —O(CH₂)₀₋₁Ph, or a 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur. Suitabledivalent substituents on a saturated carbon atom of R^(∘) include ═O and═S.

Suitable divalent substituents on a saturated carbon atom of an“optionally substituted” group include the following: ═O, ═S, ═NNR*₂,═NNHC(O)R*, ═NNHC(O)OR*, ═NNHS(O)₂R*, ═NR*, ═NOR*, —O(C(R*₂))₂₋₃O—, or—S(C(R*₂))₂₋₃S—, wherein each independent occurrence of R* is selectedfrom hydrogen, C₁₋₆ aliphatic which may be substituted as defined below,or an unsubstituted 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur. Suitable divalent substituents that are bound tovicinal substitutable carbons of an “optionally substituted” groupinclude: —O(CR*₂)₂₋₃O—, wherein each independent occurrence of R* isselected from hydrogen, C₁₋₆ aliphatic which may be substituted asdefined below, or an unsubstituted 5-6-membered saturated, partiallyunsaturated, or aryl ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R* include halogen,—R^(●), -(haloR^(●)), —OH, —OR^(●), —O(haloR^(●)), —CN, —C(O)OH,—C(O)OR^(●), —NH₂, —NHR^(●), —NR^(●) ₂, or —NO₂, wherein each R^(●) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

Suitable substituents on a substitutable nitrogen of an “optionallysubstituted” group include —R^(†), —NR^(†) ₂, —C(O)R^(†), —C(O)OR^(†),—C(O)C(O)R^(†), —C(O)CH₂C(O)R^(†), —S(O)₂R^(†), —S(O)₂NR^(†) ₂,—C(S)NR^(†) ₂, —C(NH)NR^(†) ₂, or —N(R^(†))S(O)₂R^(†); wherein eachR^(†) is independently hydrogen, C₁₋₆ aliphatic which may be substitutedas defined below, unsubstituted —OPh, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur, or,notwithstanding the definition above, two independent occurrences ofR^(†), taken together with their intervening atom(s) form anunsubstituted 3-12-membered saturated, partially unsaturated, or arylmono- or bicyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R^(†) are independentlyhalogen, —R^(●), -(haloR^(●)), —OH, —OR^(●), —O(haloR^(●)), —CN,—C(O)OH, —C(O)OR^(●), —NH₂, —NHR^(●), —NR^(●) ₂, or —NO₂, wherein eachR^(●) is unsubstituted or where preceded by “halo” is substituted onlywith one or more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

When substituents are described herein, the term “radical” or“optionally substituted radical” is sometimes used. In this context,“radical” means a moiety or functional group having an availableposition for attachment to the structure on which the substituent isbound. In general the point of attachment would bear a hydrogen atom ifthe substituent were an independent neutral molecule rather than asubstituent. The terms “radical” or “optionally-substituted radical” inthis context are thus interchangeable with “group” or“optionally-substituted group”.

As used herein, the “term head-to-tail” or “HT”, refers to theregiochemistry of adjacent repeating units in a polymer chain. Forexample, in the context of poly(propylene carbonate) (PPC), the termhead-to-tail based on the three regiochemical possibilities depictedbelow:

The term “head-to-tail ratio” or (H:T) refers to the proportion ofhead-to-tail linkages to the sum of all other regiochemicalpossibilities. With respect to the depiction of polymer structures,while a specific regiochemical orientation of monomer units may be shownin the representations of polymer structures herein, this is notintended to limit the polymer structures to the regiochemicalarrangement shown but is to be interpreted to encompass allregiochemical arrangements including that depicted, the oppositeregiochemistry, random mixtures, isotactic materials, syndiotacticmaterials, racemic materials, and/or enantioenriched materials andcombinations of any of these unless otherwise specified.

As used herein the term “alkoxylated” means that one or more functionalgroups on a molecule (usually the functional group is an alcohol, amine,or carboxylic acid, but is not strictly limited to these) has appendedto it a hydroxy-terminated alkyl chain. Alkoxylated compounds maycomprise a single alkyl group or they may be oligomeric moieties such ashydroxyl-terminated polyethers. Alkoxylated materials can be derivedfrom the parent compounds by treatment of the functional groups withepoxides.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 Shows a chart of the load bearing (CFD) data from PU foams withand without 58-103-C Polyol. Load-Bearing Properties of PU foams basedon Novomer 58-103-C Polyol (Tables 3A and 3B).

FIG. 2 Shows a chart of the load bearing (CFD) data from PU foams withand without 74-276 Polyol. Load Bearing Properties of PU foams based onNovomer 74-276 Polyol (Table 4).

FIG. 3 Shows a chart of the density-normalized load bearing data from PUfoams with and without additives of the present invention and with otheradditives. Load-Bearing Properties (Normalized Values) of PU foams basedon commericial and Novomer polyols (Tables 3-5).

FIG. 4 Shows a chart of the comfort factor data (SAG value) for PU foamswith and without additives of the present invention and with otheradditives. SAG factor of PU foams based on Novomer and commercialpolyols (Tables 3-5).

FIG. 5 Shows a chart of the comfort factor data (SAG value) for PU foamswith and without additives of the present invention and with otheradditives. SAG factor of PU foams based on Novomer and commercialpolyols (Tables 3-5).

FIG. 6 Shows a graph comparing CFD values for certain viscoelastic (VE)foams of the present invention with reference foams. Effect of NovomerPPC-0.8-DPG (polyol 74-217) on CFD of viscoelastic foams:REF-3—Reference foam (#1 in Tables 2B-5B); CaCO₃-2—Reference foamprepared with CaCO₃ as filler (#2 in Tables 2B-5B); PPC-0.8-DPG-10%—Foamprepared with 10% Novomer polyol (#3 in Table 3B); Foam 1—Foam preparedwith 10% Novomer polyol and CaCO₃ as filler (#5 in Table 3B).

FIG. 7 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Normalized CFD values forreference visco-elastic foams and visco-elastic foams based onPPC-0.8-DPG Novomer polyol (74-217): REF-3—Reference foam (#1 in Tables2B-5B); CaCO₃-2—Reference foam prepared with CaCO₃ as filler (#2 inTables 2B-5B); PPC-0.8-DPG-10%—Foam prepared with 10% Novomer polyol (#3in Table 3B); Foam 1—Foam prepared with 10% Novomer polyol and CaCO₃ asfiller (#5 in Table 3B).

FIG. 8 Shows a graph comparing hysteresis of certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-0.8-DPGpolyol (74-217) on Hysteresis of viscoelastic foams: REF-3—Referencefoam (#1 in Tables 2B-5B); CaCO₃-2—Reference foam prepared with CaCO₃ asfiller (#2 in Tables 2B-5B); PPC-0.8-DPG-10%—Foam prepared with 10%Novomer polyol 74-217 (#3 in Table 3B); Foam 1—Foam prepared with 10%Novomer polyol 74-217 and CaCO₃ as filler (#5 in Table 3B).

FIG. 9 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-0.9-DPG(74-217) polyol on CFD of viscoelastic foams: REF-3—Reference foam (#1in Tables 2B-5B); PPC-0.8-DPG-10%—Foam prepared with 10% Novomer polyol74-217 (#3 in Table 3B); PPC-0.8-DPG-20%—Foam prepared with 20% Novomerpolyol 74-217 (#4 in Table 3B).

FIG. 10 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Normalized CFD values forreference foams and foams based on Novomer PPC-0.8-DPG polyol (74-217):REF-3—Reference foam (#1 in Tables 2-5); PPC-0.8-DPG-10%—Foam preparedwith 10% Novomer polyol 74-217 (#3 in Table 3).

FIG. 11 Shows a graph comparing hysteresis of certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-0.8-DPG(74-217) polyol on Hysteresis of viscoelastic foams: REF-3—Referencefoam (#1 in Tables 2B-5B); PPC-0.8-DPG-10%—Foam prepared with 10%Novomer polyol 74-217 (#3 in Table 3B); PPC-0.8-DPG-20%—Foam preparedwith 20% Novomer polyol 74-217 (#4 in Table 3B).

FIG. 12 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-1.2-DPGpolyol (58-103-C) on CFD viscoelastic foams: REF-3—Reference foam (#1 inTables 2B-5B); Novomer 103C-4—Foam prepared with 10% Novomer polyol58-103-C(#6 in Table 2B-1); Novomer 103C-5—Foam prepared with 18%Novomer polyol 58-103-C(#3 in Table 2B-2).

FIG. 13 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Normalized CFD values forreference VE foams and VE foams based on Novomer PPC-1.2-DPG (58-103-C)polyol: REF-3—Reference foam (#1 in Tables 2B-5B); Novomer 103C-4—Foamprepared with 10% Novomer polyol 58-103C (#6 in Table 2B-1); Novomer103C-5—Foam prepared with 18% Novomer polyol 58-103-C(#3 in Table 2B-2).

FIG. 14 Shows a graph comparing hysteresis of certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-1.2-DPGpolyol (58-103-C) on Hysteresis of viscoelastic foams: REF-3—Referencefoam (#1 in Tables 2B-5B); Novomer 103-4—Foam prepared with 10% Novomerpolyol 58-103-C(#6 in Table 2B-1); Novomer 103C-5—Foam prepared with 18%Novomer polyol 58-103-C(#3 in Table 2B-2).

FIG. 15 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-2.3-PEOLpolyol (74-277) on CFD of viscoelastic foams: REF-3—Reference foam (#1in Tables 2B-5B); PPC-2.3-PEOL-10%—Foam prepared with 10% of Novomerpolyol 74-277 (#3 in Tables 4B); PPC-2.3-PEOL-20%—Foam prepared with 20%Novomer polyol 74-277 (#4 in Table 4B).

FIG. 16 Shows a graph comparing CFD values for certain VE foams of thepresent invention with reference foams. Normalized CFD values forreference VE foams and VE foams based on Novomer PPC-2.3-PEOL (74-277)polyol: REF-3 Reference foam (#1 in Tables 2B-5B); PPC-2.3-PEOL-10%—Foamprepared with 10% Novomer polyol 74-277 (#3 in Table 4B);PPC-2.3-PEOL-20%—Foam prepared with 20% Novomer polyol 74-277 (#4 inTable 4B).

FIG. 17 Shows a graph comparing hysteresis of certain VE foams of thepresent invention with reference foams. Effect of Novomer PPC-2.3-PEOLpolyol on Hysteresis of viscoelastic foams: REF-3—Reference foam (#1 inTables 2B-5B); PPC-2.3-PEOL-10%—Foam prepared with 10% Novomer polyol74-277 (#3 in Table 4B); PPC-2.3-PEOL-20%—Foam prepared with 20% Novomerpolyol 74-277 (#4 in Table 4B).

FIG. 18A Shows DMA graphs for a reference VE foam and a VE foam preparedaccording to the present invention. DMA graph of reference foam(Formulation #1 in Tables 2B-5B).

FIG. 18B Shows DMA graphs for a reference VE foam and a VE foam preparedaccording to the present invention. DMA graph of foam prepared withNovomer polyol 74-217 (Formulation #4 in Table 3B).

FIG. 19A Shows DMA graphs for two VE foam samples prepared according tothe present invention. DMA graph of foam prepared with Novomer 58-103-Cpolyol (Formulation #3 in Table 2B-1).

FIG. 19B Shows DMA graphs for two VE foam samples prepared according tothe present invention. DMA graph of foam prepared with Novomer 58-103-Cpolyol (Formulation #4 in Table 4B).

FIG. 20A Shows DMA graphs for two VE foam samples prepared according tothe present invention. DMA graph of foam prepared with a mixture ofthree different Novomer polyols (Formula #5 in Table 5B).

FIG. 20B Shows DMA graphs for two VE foam samples prepared according tothe present invention. DMA graph of foam prepared with a mixture ofthree different Novomer Polyols (Formulation #6 in Table 5B).

FIG. 21A Shows DSC graphs for a reference VE foam and a VE foam preparedaccording to the present invention. DSC graph of reference foam(Formulation #1 in Tables 2B-5B).

FIG. 21B Shows DSC graphs for a reference VE foam and a VE foam preparedaccording to the present invention. DSC graph of foam prepared withNovomer polyol 74-217 (Formulation #4 in Table 3B).

FIG. 22A Shows DSC graphs for two VE foam samples prepared according tothe present invention. DSC graph of foam prepared with Novomer polyol58-103-C (Formulation #3 in Table 2B-1).

FIG. 22B Shows DSC graphs for two VE foam samples prepared according tothe present invention. DSC graph of foam prepared with Novomer polyol74-277 (Formulation #4 in Table 4B).

FIG. 23A Shows DSC graphs for two VE foam samples prepared according tothe present invention. DSC graph of foam prepared with a mixture ofthree different Novomer Polyols (Formulation #5 in Table 5B).

FIG. 23B Shows DSC graphs for two VE foam samples prepared according tothe present invention. DSC graph of foam prepared with a mixture ofthree different Novomer Polyols (Formulation #6 in Table 5B).

FIG. 24 Shows a chart of the resilience properties of PU foams based onNovomer and Commercial Polyols.

FIG. 25 Shows a chart of the hysteresis properties of PU foams based onNovomer and Commercial Polyols.

FIG. 26 Shows a chart of the load bearing properties of PU foams basedon Novomer and Commercial Polyols.

FIG. 27 Shows a chart of the load bearing properties of PU foams basedon Novomer and Commercial Polyols.

FIG. 28 Shows a chart of the load bearing properties of PU foams basedon Novomer and Commercial Polyols.

FIG. 29 Shows a chart of the Normalized load bearing properties of PUfoams based on Novomer and Commercial Polyols.

FIG. 30 Shows a chart of the Normalized load bearing properties of PUfoams based on Novomer and Commercial Polyols.

FIG. 31 Shows a chart of the Normalized load bearing properties of PUfoams based on Novomer and Commercial Polyols.

FIG. 32 Shows a chart of support factor data for PU foams based onNovomer and Commercial Polyols.

FIG. 33 Shows Chrysler Material Standard: MS-DC-649 for “Cellular,Molded Polyurethane High Resilient (HR) Type Seat Applications”.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

The field of polyurethane manufacture and formulation is well advanced.In some embodiments, the novel materials presented herein areformulated, processed, and used according to methods well known in theart. Combining knowledge of the art, with the disclosure and teachingsherein, the skilled artisan will readily apprehend variations,modifications and applications of the compositions and such variationsare specifically encompassed herein. The following references containinformation on the formulation, manufacture and uses of polyurethanefoams and elastomers, the entire content of each of these references isincorporated herein by reference.

-   Vahid Sendijarevic, et al.; Polymeric Foams And Foam Technology,    2^(nd) edition, Hanser Gardner Publications; 2004 (ISBN    978-1569903360)-   David Eaves; Handbook of Polymer Foams, Smithers Rapra Press; 2004    (ISBN 978-1859573884)-   Shau-Tarng Lee et al.; Polymeric Foams: Science and Technology, CRC    Press 2006 (ISBN 978-0849330759)-   Kaneyoshi Ashida; Polyurethane and Related Foams: Chemistry and    Technology, CRC Press; 2006 (ISBN 978-1587161599)-   Handbook of Thermoplastic Elastomers, William Andrew Publishers,    2007 (ISBN 978-0815515494)-   The Polyurethanes Book, J. Wiley & Sons, 2003 (ISBN 978-0470850411)

I. METHODS OF STRENGTHENING POLYURETHANE FOAMS

Commercial polyurethane foam compositions are typically manufactured bycombining two components: an isocyanate component containing one or morepolyisocyanate compounds optionally blended with additional materialssuch as diluents, solvents, coreactants and the like (often referred toin the art as an A-side mixture), and a polyol component comprising oneor more polyols optionally blended with additional reactants, solvents,catalysts, or additives (typically referred to in the art as the B sidemixture).

In certain embodiments, methods of the present invention include a stepof substituting a portion of the polyol component of a polyurethane foamcomposition with a strength enhancing additive comprising an aliphaticpolycarbonate polyol derived from the copolymerization of CO₂ and one ormore epoxides.

In certain embodiments, the method entails replacing between about 1weight and about 50 weight percent of the polyol content of apolyurethane foam formulation with an aliphatic polycarbonate polyol. Incertain embodiments, the aliphatic polycarbonate polyol used for thispurpose has a primary polymer repeat unit with the structure:

wherein R¹ is, at each occurrence in the polymer chain, independently—H, —CH₃, or —CH₂CH₃.

In certain embodiments, the present invention provides a method forincreasing the load bearing properties of a polyurethane foamcomposition, the foam composition comprising the reaction product of apolyol component and a polyisocyanate component, the method comprisingthe step of incorporating into the polyol component a polycarbonatepolyol derived from the copolymerization of one or more epoxides andcarbon dioxide. In certain embodiments, the polycarbonate polyol isadded in a quantity from about 1 weight percent to about 50 weightpercent of all polyols present in the polyol component of the foamformulation. In certain embodiments, the added polycarbonate polyol isprovided in a quantity from about 2 weight percent to about 50 weightpercent of all polyols present in the polyol component of the foamformulation. In certain embodiments, the added polycarbonate polyol isprovided in a quantity from about 5 weight percent, to about 25 weightpercent of all polyol present in the polyol component. In certainembodiments, the added polycarbonate polyol is provided in a quantityfrom about 1 weight percent to about 2 weight percent of all polyolpresent in the polyol component. In certain embodiments, the addedpolycarbonate polyol is provided in a quantity from about 2 weightpercent to about 5 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the added polycarbonate polyol isprovided in a quantity from about 2 weight percent to about 10 weightpercent of all polyol present in the polyol component. In certainembodiments, the added polycarbonate polyol is provided in a quantityfrom about 5 weight percent to about 10 weight percent of all polyolpresent in the polyol component. In certain embodiments, the addedpolycarbonate polyol is provided in a quantity from about 10 weightpercent, to about 20 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the added polycarbonate polyol isprovided in a quantity from about 20 weight percent, to about 30 weightpercent of all polyol present in the polyol component. In certainembodiments, the added polycarbonate polyol is provided in a quantityfrom about 30 weight percent, to about 50 weight percent of all polyolpresent in the polyol component. In certain embodiments, the addedpolycarbonate polyol is provided in a quantity of about 1 weight percentof all polyol present in the polyol component. In certain embodiments,the added polycarbonate polyol is provided in a quantity of about 2weight percent of all polyol present in the polyol component. In certainembodiments, the added polycarbonate polyol is provided in a quantity ofabout 3 weight percent of all polyol present in the polyol component. Incertain embodiments, the added polycarbonate polyol is provided in aquantity of about 5 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the added polycarbonate polyol isprovided in a quantity of about 10 weight percent of all polyol presentin the polyol component. In certain embodiments, the added polycarbonatepolyol is provided in a quantity of about 15 weight percent of allpolyol present in the polyol component. In certain embodiments, theadded polycarbonate polyol is provided in a quantity of about 20 weightpercent of all polyol present in the polyol component. In certainembodiments, the added polycarbonate polyol is provided in a quantity ofabout 25 weight percent of all polyol present in the polyol component.In certain embodiments, the added polycarbonate polyol is provided in aquantity of about 30 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the added polycarbonate polyol isprovided in a quantity of about 40 weight percent of all polyol presentin the polyol component.

In certain embodiments, the other polyols present in the polyolcomponent to which the aliphatic polycarbonate polyol is added areselected from the group consisting of: polyether polyols, polyesterpolyols, polybutadiene polyols, polysulfide polyols, natural oilpolyols, fluorinated polyols, aliphatic polyols, polyethercarbonatepolyols, polycarbonate polyols other than those derived from epoxide-CO₂copolymerization, and mixtures of any two or more these. In certainembodiments, between about 50 percent and about 99 percent of the totalweight of polyol present in the polyol component (i.e. exclusive of anyother non-polyol components that may be present in a B-side compositionfor foams such as catalysts, cell openers, blowing agents, stabilizers,diluents, pigments and the like) comprises one or more polyols selectedfrom the group consisting of polyether polyols, polyester polyols,polybutadiene polyols, polysulfide polyols, natural oil polyols,fluorinated polyols, aliphatic polyols, polycarbonate polyols other thanthose derived from epoxide-CO₂ copolymerization, and mixtures of any twoor more these. In certain embodiments, the other polyol present in thepolyol component to which the aliphatic polycarbonate polyol is addedsubstantially comprises polyether polyol. In certain embodiments, theother polyol present in the polyol component to which the aliphaticpolycarbonate polyol is added substantially comprises polyester polyol.In certain embodiments, the other polyols present in the polyolcomponent to which the aliphatic polycarbonate polyol is addedsubstantially comprise a mixture of polyether and polyester polyols.

In certain embodiments, methods of the present invention compriseformulating a high strength flexible polyurethane foam composition byproviding a polycarbonate polyol derived from the copolymerization ofone or more epoxides and carbon dioxide as a polyol component in aB-side composition comprising a polyether polyol. In certain embodimentsthe polycarbonate polyol is provided in such a quantity that the finalB-side composition contains from about 1 part to about 100 parts byweight of polycarbonate polyol based on 100 parts of polyether polyol.In certain embodiments, the polycarbonate polyol is added in such aquantity that the polycarbonate polyol comprises about 5 parts, about 10parts, about 20 parts, about 30 parts, about 40 parts, about 60 parts,about 80 parts, or about 100 parts, based on 100 parts of polyetherpolyol in the resulting B-side formulation. In certain embodiments, thealiphatic polycarbonate polyol comprises poly(propylene carbonate). Incertain embodiments, the aliphatic polycarbonate polyol added comprisespoly(ethylene carbonate). In certain embodiments, the aliphaticpolycarbonate polyol added comprises poly(ethylene-co-propylenecarbonate). In certain embodiments, the method comprises the additionalsteps of stirring and/or heating a mixture of the aliphaticpolycarbonate polyol and the polyether polyol. In certain embodiments,the method comprising the step of stirring and/or heating is performeduntil a substantially homogenous mixture of the polycarbonate polyol andthe polyether polyol is formed.

In certain embodiments, the methods of the present invention arecharacterized in that foams formulated using the methods have higherstrength than corresponding foams formulated without the step ofproviding the polycarbonate polyol. In certain embodiments, the methodsare characterized in that one or more properties selected from the groupconsisting of: Tensile Strength at Break (as measured by ASTM D3574-08Test E); Tear Strength (as measured by ASTM D3574-08 Test F);Compression Force Deflection (CFD) (as measured by ASTM D3574-08 TestC); and Tensile strength and Elongation after Dry Heat Aging for 22hours at 140° C. (as measured by ASTM D3574-08Test K) are enhancedrelative to those of a corresponding reference foam formulated withoutthe step of adding the polycarbonate polyol.

In certain embodiments, the inventive methods are characterized in thatthe foams produced have high compression force deflection. With theexisting art, such CFDs can only be achieved for flexible foams withgood comfort properties by incorporating filled polyols. The use offilled polyols can be undesirable from a cost perspective and raisesconcerns due to the presence of residual VOCs such as styrene. ResidualVOCs cause nuisance odors in the finished foams, and may have negativehealth effects for those exposed to articles made from the foam. We havefound that foams strengthened by addition of epoxide CO₂ copolymers haveCFD values as measured by ASTM D3574-08 Test C that are uniquely high,meeting or exceeding those attained by addition of filled polyols butwithout the attendant problems associated with filled polyols. Thus incertain embodiments, the present invention encompasses methods of makinghigh CFD foams.

In certain embodiments, the present invention provides methods offormulating high strength polyurethane foam compositions (denoted theStrengthened Foam formulation) comprising the step of adding apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide to a B-side formulation, the methodcharacterized in that the load bearing capacity of the strengthened foamas indicated by its compression force deflection (CFD) value measured byASTM D3574-08 Test C, is greater than the CFD value of the correspondingfoam composition formulated without the added polycarbonate polyoldenoted the Reference Foam formulation, (i.e. the comparison is betweentwo foams formulated similarly but for the substitution of thepolycarbonate polyol for a portion of the polyol present in the B-sideof the reference foam; non-limiting examples of such comparisons areprovided in the Examples section hereinbelow, importantly, for a validcomparison no other additions or substantial changes in the ratios oridentities of the other foam components are made). In certainembodiments, the method comprises adding the aliphatic polycarbonatepolyol to the B-side formulation by substituting a portion of one ormore polyols in the reference formulation such that the —OH number ofthe B-side formulation for the strengthened foam is substantially thesame as that of the B-side formulation of the reference foamformulation. In certain embodiments, the method is characterized in thatthe CFD value of the strengthened foam formulation is at least 10%greater than the CFD value of the reference foam formulation. In certainembodiments, the method is characterized in that the CFD value of thestrengthened foam formulation is at least 10% greater, at least 20%greater, at least 30% greater, at least 40% greater, at least 50%greater, or at least 100% greater than the CFD value of the referencefoam. In certain embodiments, the CFD values of the strengthened foamand the reference foam are normalized for the density of the foam priorto comparing them. In certain embodiments the method is characterized inthat the strengthened foam composition and the reference foamcomposition have substantially the same density.

In certain embodiments, the present invention provides methods offormulating high strength polyurethane foam compositions (denoted thestrengthened foam formulation) comprising the step of adding apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide to a B-side formulation, the methodcharacterized in that the strengthened foam formulation has a lowerdensity than the corresponding foam composition formulated without theadded polycarbonate polyol (denoted the reference foam formulation)further characterized in that the load bearing properties (CFD) of thestrengthened foam as determined by ASTM D3574-08 Test C, are equal to orgreater than those of the reference foam. In certain embodiments, themethod comprises adding the aliphatic polycarbonate polyol to the B-sideformulation by substituting a portion of one or more polyols in thereference formulation such that the —OH number of the B-side formulationfor the strengthened foam is substantially the same as that of theB-side formulation of the reference foam formulation. In certainembodiments, the method is characterized in that the density of thestrengthened foam formulation is at least 10% lower than the density ofthe reference foam formulation. In certain embodiments, the method ischaracterized in that the density of the strengthened foam formulationis at least 10%, at least 20%, at least 30%, at least 40%, or at least50%, less than the density of the reference foam. In certainembodiments, the method is characterized in that the density of thestrengthened foam formulation is at least 10%, at least 20%, at least30%, at least 40%, or at least 50%, less than the density of thereference foam while the CFD of the strengthened foam is at least equalto, at least 10% greater than, at least 20% greater than, at least 30%greater than, at least 40% greater than, at least 50% greater than, atleast 75% greater than, or at least 100% greater than the CFD of thereference foam.

In certain embodiments, the method is characterized in that theStrengthened Foam formulation has the combination of a density of lessthan about 2.6 pounds/cubic foot (pcf) and a CFD as measured by ASTMD3574-08 Test C of at least 0.4 psi at 25% deflection. In certainembodiments, the method is characterized in that the CFD value is atleast 0.45 psi at 25% deflection, at least 0.5 psi at 25% deflection, orat least 0.52 psi at 25% deflection. In certain embodiments, the methodis characterized in that the CFD value of the strengthened foamformulation measured by ASTM D3574-08 Test C is at least 0.5 psi at 50%deflection. In certain embodiments, the method is characterized in thatthe CFD value of the strengthened foam formulation measured by ASTMD3574-08 Test C is at least 0.55 psi at 50% deflection, at least 0.60psi at 50% deflection, at least 0.65 psi at 50% deflection, at least 0.7psi at 50% deflection, or at least 0.75 psi at 50% deflection. Incertain embodiments, the method is characterized in that the CFD valueof the strengthened foam formulation measured by ASTM D3574-08 Test C isat least 0.7 psi at 65% deflection. In certain embodiments, the methodis characterized in that the CFD value of the strengthened foamformulation measured by ASTM D3574-08 Test C is at least 0.75 psi at 65%deflection, at least 0.80 psi at 65% deflection, at least 0.85 psi at65% deflection, at least 0.9 psi at 65% deflection, or at least 1 psi at65% deflection. In certain embodiments, the CFD values above are for afoam composition having a density of between about 2 and 2.6 pcf. Incertain embodiments, the CFD values above are for a foam compositionhaving a density of between about 2.2 and 2.6 pcf, or a density of about2.4 pcf. In certain embodiments, the CFD values above are for foamshaving a density between about 2 and 2.6 pcf and further characterizedin that they contain less than 10% filled polyol, less than 5% filledpolyol, less than 3% filled polyol, less than 2% filled polyol, lessthan 1% filled polyol, or characterized in that they are substantiallyfree of filled polyol. In certain embodiments, the foam formulationsabove are characterized in that they have comfort properties suitablefor use in seating foams.

In certain embodiments, the method is characterized in that theStrengthened Foam formulation has the combination of a density of lessthan about 4 pcf and a CFD as measured by ASTM D3574-08 Test C of atleast 0.8 psi at 25% deflection. In certain embodiments, the method ischaracterized in that the CFD value of the strengthened foam formulationis at least 0.85 psi at 25% deflection, at least 0.9 psi at 25%deflection, at least 0.95 psi at 25% deflection, or at least 1 psi at25% deflection. In certain embodiments, the method is characterized inthat the CFD value of the strengthened foam formulation with a densityof less than about 4 pcf as measured by ASTM D3574-08 Test C is at least1 psi at 50% deflection. In certain embodiments, the method ischaracterized in that the CFD value is at least 1.1 psi at 50%deflection, at least 1.2 psi at 50% deflection, at least 1.3 psi at 50%deflection, or at least 1.4 psi at 50% deflection. In certainembodiments, the method is characterized in that the CFD value of thestrengthened foam formulation with a density of less than about 4 pcf asmeasured by ASTM D3574-08 Test C is at least 1.4 psi at 65% deflection.In certain embodiments, the method is characterized in that the CFDvalue of the strengthened foam formulation is at least 1.5 psi at 65%deflection, at least 1.6 psi at 65% deflection, at least 1.7 psi at 65%deflection, at least 1.8 psi at 65% deflection, at least 1.9 psi at 65%deflection, or at least 2 psi at 65% deflection. In certain embodiments,the CFD values above are for a foam composition having a density ofbetween about 3.2 and 3.8 pcf. In certain embodiments, the CFD valuesabove are for a foam composition having a density of between about 3.3and 3.7 pcf, or a density of about 3.5 pcf. In certain embodiments, theCFD values above are for foams having a density between about 3.2 and3.8 pcf and further characterized in that they contain less than 10%filled polyol, less than 5% filled polyol, less than 3% filled polyol,less than 2% filled polyol, less than 1% filled polyol, or characterizedin that they are substantially free of filled polyol. In certainembodiments, the foam formulations above are characterized in that theyhave comfort properties suitable for use in seating foams. In certainembodiments, the present invention provides methods of formulating highstrength polyurethane foam compositions (denoted the strengthened foamformulation) comprising the step of adding a polycarbonate polyolderived from the copolymerization of one or more epoxides and carbondioxide to a B-side formulation, the method characterized in that thetensile strength of the strengthened foam as measured by ASTM D 3574-08Test E, is greater than the tensile strength of the corresponding foamcomposition formulated without the added polycarbonate polyol (denotedthe reference foam formulation). In certain embodiments, the methodcomprises adding the aliphatic polycarbonate polyol to the B-sideformulation by substituting a portion of one or more polyols in thereference formulation such that the —OH number of the B-side formulationfor the strengthened foam is substantially the same as that of theB-side formulation of the reference foam formulation. In certainembodiments, the method is characterized in that the tensile strength ofthe strengthened foam formulation is at least 10% greater than thetensile strength of the reference foam formulation. In certainembodiments, the method is characterized in that the tensile strength ofthe strengthened foam formulation is at least 20%, at least 30%, atleast 40%, at least 50%, or at least 100% greater than the tensilestrength of the reference foam. In certain embodiments, the tensilestrengths of the strengthened foam and the reference foam are normalizedfor the density of the foams prior to comparing them. In certainembodiments the method is characterized in that the strengthened foamcomposition and the reference foam composition have substantially thesame density.

In certain embodiments, the present invention provides methods offormulating high strength polyurethane foam compositions (denoted thestrengthened foam formulation) comprising the step of adding apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide to a B-side formulation, the methodcharacterized in that the strengthened foam formulation has a lowerdensity than the corresponding foam composition formulated without theadded polycarbonate polyol (denoted the reference foam formulation)further characterized in that the tensile strength of the strengthenedfoam as determined by ASTM D3574-08 Test E is equal to or greater thanthat of the reference foam. In certain embodiments, the method comprisesadding the aliphatic polycarbonate polyol to the B-side formulation bysubstituting a portion of one or more polyols in the referenceformulation such that the —OH number of the B-side formulation for thestrengthened foam is substantially the same as that of the B-sideformulation of the reference foam formulation. In certain embodiments,the method is characterized in that the density of the strengthened foamformulation is at least 10% lower than the density of the reference foamformulation. In certain embodiments, the method is characterized in thatthe density of the strengthened foam formulation is at least 10%, atleast 20%, at least 30%, at least 40%, or at least 50%, less than thedensity of the reference foam. In certain embodiments, the method ischaracterized in that the density of the strengthened foam formulationis at least 10%, at least 20%, at least 30%, at least 40%, or at least50%, less than the density of the reference foam while the tensilestrength of the strengthened foam is at least equal to, at least 10%greater than, at least 20% greater than, at least 30% greater than, atleast 40% greater than, at least 50% greater than, at least 75% greaterthan, or at least 100% greater than the tensile strength of thereference foam.

In certain embodiments, the present invention provides methods offormulating high strength polyurethane foam compositions (denoted thestrengthened foam formulation) comprising the step of adding apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide to a B-side formulation, the methodcharacterized in that the tear strength of the strengthened foam asmeasured by ASTM D 3574-08 Test F is greater than the tear strength ofthe corresponding foam composition formulated without the addedpolycarbonate polyol (denoted the reference foam formulation). Incertain embodiments, the method comprises adding the aliphaticpolycarbonate polyol to the B-side formulation by substituting a portionof one or more polyols in the reference formulation such that the —OHnumber of the B-side formulation for the strengthened foam issubstantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the method ischaracterized in that the tensile strength of the strengthened foamformulation is at least 10% greater than the tensile strength of thereference foam formulation. In certain embodiments, the method ischaracterized in that the tear strength of the strengthened foamformulation is at least 20%, at least 30%, at least 40%, at least 50%,or at least 100% greater than the tear strength of the reference foam.In certain embodiments, the tear strengths of the strengthened foam andthe reference foam are normalized for the density of the foams prior tocomparing them. In certain embodiments the method is characterized inthat the strengthened foam composition and the reference foamcomposition have substantially the same density.

In certain embodiments, the present invention provides methods offormulating high strength polyurethane foam compositions (denoted thestrengthened foam formulation) comprising the step of adding apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide to a B-side formulation, the methodcharacterized in that the strengthened foam formulation has a lowerdensity than the corresponding foam composition formulated without theadded polycarbonate polyol (denoted the reference foam formulation)further characterized in that the tear strength of the strengthened foamas determined by ASTM D3574-08 Test F is equal to or greater than thatof the reference foam. In certain embodiments, the method comprisesadding the aliphatic polycarbonate polyol to the B-side formulation bysubstituting a portion of one or more polyols in the referenceformulation such that the —OH number of the B-side formulation for thestrengthened foam is substantially the same as that of the B-sideformulation of the reference foam formulation. In certain embodiments,the method is characterized in that the density of the strengthened foamformulation is at least 10% lower than the density of the reference foamformulation. In certain embodiments, the method is characterized in thatthe density of the strengthened foam formulation is at least 10%, atleast 20%, at least 30%, at least 40%, or at least 50%, less than thedensity of the reference foam. In certain embodiments, the method ischaracterized in that the density of the strengthened foam formulationis at least 10%, at least 20%, at least 30%, at least 40%, or at least50%, less than the density of the reference foam while the tear strengthof the strengthened foam is at least equal to, at least 10% greaterthan, at least 20% greater than, at least 30% greater than, at least 40%greater than, at least 50% greater than, at least 75% greater than, orat least 100% greater than the tear strength of the reference foam.

In certain embodiments, a strengthened foam composition made by thepreceding methods comprises a flexible polyurethane foam. In certainembodiments, a strengthened foam composition made by the precedingmethods comprises a viscoelastic polyurethane foam. In certainembodiments, a strengthened foam composition made by the precedingmethods comprises a rigid polyurethane foam.

In certain embodiments, a polycarbonate polyol utilized in the methodsdescribed above has a primary repeating unit having a structure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

In certain embodiments, the polycarbonate polyols utilized in themethods described above contain a primary repeating unit having astructure:

where R¹ is as defined above.

In certain embodiments, a polycarbonate polyol utilized in the methodsdescribed above contains a primary repeating unit having a structure:

wherein R¹ is, at each occurrence in the polymer chain, independently—H, or —CH₃.

In certain embodiments, the polycarbonate polyol utilized in the methodsdescribed above is characterized in that it has a number averagemolecular weight (Mn) between about 500 g/mol and about 20,000 g/mol. Incertain embodiments, the polycarbonate polyol is characterized in thatit has an Mn between about 1,000 g/mol and about 5,000 g/mol. In certainembodiments, the polycarbonate polyol is characterized in that it has anMn between about 1,000 g/mol and about 3,000 g/mol. In certainembodiments, the polycarbonate polyol is characterized in that it has anMn of about 1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about2,000 g/mol, about 2,500 g/mol or about 3,000 g/mol.

In certain embodiments, the polycarbonate polyol utilized in the methodsdescribed above is characterized in that it has a high percentage of endgroups reactive toward isocyanates. In certain embodiments, more than98%, more than 99%, more than 99.5%, more than 99.8%, more than 99.9%,or essentially 100% of the chain ends are groups reactive towardisocyanates. In certain embodiments, the chain ends reactive towardisocyanates comprise —OH groups.

In certain embodiments, aliphatic polycarbonate polyols utilized in themethods described above are characterized in that they are substantiallycompatible with or soluble in the other polyols present in the polyolcomponent of the foam formulations. Substantially compatible in thiscontext means that the aliphatic polycarbonate can be mixed with theother polyol or polyols and provide a mixture that is homogenous ornearly homogenous. In certain embodiments, the mixture is largelyhomogenous at ambient temperature while in other embodiments, themixture is homogenous at elevated temperatures (for example the mixtureis homogenous at 30° C., at 40° C., at 80° C., at 100° C. or at 140°C.). In certain embodiments, the polyol component of the foamformulation containing the aliphatic polycarbonate polyol ischaracterized in that it is a substantially homogenous transparentmixture.

In certain embodiments, the structure of the aliphatic polycarbonatepolyol used in the methods above is chosen to enhance its compatibilitywith other polyols in the polyol component of the foam formulation. Incertain embodiments, a provided aliphatic polycarbonate polyol ischaracterized in that it has one or more ether linkages present in achain transfer agent embedded within the polycarbonate chain. In certainembodiments, such ether linkages derive from the use of diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols, orpolyethylene-co-propylene glycols as chain transfer agents in thepreparation of the aliphatic polycarbonate polyol. In certainembodiments, such ether linkages are provided by utilizing ethoxylatedor propolxylated diols, triols, or higher polyhydric alcohols havingfour or more —OH groups. In certain embodiments, such ether linkages areprovided by utilizing isosorbide, or other carbohydrate-derivedmaterials as chain transfer agents.

In certain embodiments, a provided aliphatic polycarbonate polyol ischaracterized in that it has a functional number of 2. In certainembodiments provided aliphatic polycarbonate polyols have a functionalnumber greater than 2. In certain embodiments provided aliphaticpolycarbonate polyols have a functional number between 2 and 4. Incertain embodiments provided aliphatic polycarbonate polyols have afunctional number between 2 and 3. In certain embodiments providedaliphatic polycarbonate polyols have a functional number between 2 andabout 2.6, between 2 and about 2.5, or between 2 and about 2.4. Incertain embodiments, the provided aliphatic polycarbonate polyol ischaracterized in that it comprises a mixture of diol (functional number2) with a higher functional polyol (e.g. a polyol with a functionalnumber of 3, 4, 5, or 6).

In certain embodiments, a provided aliphatic polycarbonate polyol ischaracterized in that it has a number average molecular weight (Mn) lessthan about 10,000 g/mol. In certain embodiments, a provided aliphaticpolycarbonate polyol is characterized in that it has an Mn between 400and about 10,000 g/mol. In certain embodiments, a provided aliphaticpolycarbonate polyol is characterized in that it has an Mn between 400and about 5,000 g/mol, between 500 and about 3,000 g/mol, between 700and about 2,500 g/mol, between 1,000 and 3,000 g/mol, or between 700 and1500 g/mol.

In certain embodiments, a provided aliphatic polycarbonate polyol ischaracterized in that it comprises a copolymer of carbon dioxide and oneor both of ethylene oxide and propylene oxide having an Mn less than10,000 g/mol, a functional number between 2 and 4, and having one ormore ether linkages present in a chain transfer agent embedded withinthe polycarbonate chain. In certain embodiments, a providedpolycarbonate polyol comprises poly(propylene carbonate) containing anembedded chain transfer agent derived from diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, higherpolyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 5,000 g/mol, and afunctional number between 2 and 3. In certain embodiments, a providedpolycarbonate polyol comprises poly(propylene carbonate) containing anembedded chain transfer agent derived from diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, higherpolyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 3,000 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, a providedpolycarbonate polyol comprises poly(propylene carbonate) containing anembedded chain transfer agent derived from diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, higherpolyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn between 500 and 2,500 g/mol, and afunctional number between 2 and 2.5.

In certain embodiments, a provided polycarbonate polyol comprisespoly(ethylene carbonate) containing an embedded chain transfer agentderived from diethylene glycol, dipropylene glycol, triethylene glycol,tripropylene glycol, higher polyethylene glycols, higher polypropyleneglycols, polyethylene-co-propylene glycols, or alkoxylated polyhydricalcohols, characterized in that it has an Mn less than 5,000 g/mol, anda functional number between 2 and 3. In certain embodiments, a providedpolycarbonate polyol comprises poly(ethylene carbonate) containing anembedded chain transfer agent derived from diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, higherpolyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 3,000 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, a providedpolycarbonate polyol comprises poly(ethylene carbonate) containing anembedded chain transfer agent derived from diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, higherpolyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn between 500 and 2,500 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, a providedpolycarbonate polyol comprises poly(ethylene-co-propylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 5,000 g/mol, and afunctional number between 2 and 3. In certain embodiments, a providedpolycarbonate polyol comprises poly(ethylene-co-propylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 3,000 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, a providedpolycarbonate polyol comprises poly(ethylene-co-propylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn between 500 and 2,500 g/mol, and afunctional number between 2 and 2.5.

The structures and properties of additional aliphatic polycarbonatepolyols that have utility for methods of the present invention aredescribed in Appendix A at the end of this specification entitled“Aliphatic Polycarbonate Polyols”. In certain embodiments, the presentinvention encompasses any of the methods described above, wherein theadded polycarbonate polyol is selected from any one or more of thosedescribed in Appendix A.

In certain embodiments, methods of the present invention comprise theadditional step of reacting any of the B-side mixtures containingaliphatic polycarbonate polyols described above with an A-sideformulation comprising one or more polyisocyanates.

The art of polyurethane synthesis is well advanced and a very largenumber of isocyanates and related polyurethane precursors are known inthe art and available commercially. It is to be understood that it iswithin the capabilities of one skilled in the art of polyurethaneformulation to use such isocyanates along with the teachings of thisdisclosure to practice methods within the scope of the presentinvention. Descriptions of suitable isocyanate compounds and relatedmethods can be found in: Chemistry and Technology of Polyols forPolyurethanes Ionescu, Mihail 2005 (ISBN 978-1-84735-035-0), and H.Ulrich, “Urethane Polymers,” Kirk-Othmer Encyclopedia of ChemicalTechnology, 1997 the entirety of each of which is incorporated herein byreference. In certain embodiments, the A-side formulations contain oneor more of the isocyanate reagents described in Appendix B entitledIsocyanate Reagents appearing at the end of this specification.

As an alternative to the methods above, another strategy encompassed bythe present invention involves incorporating aliphatic polycarbonatepolyols into a foam formulation by incorporating them not in the B-sidepolyol mixture, but as part of the A-side isocyanate component of thefoam. This strategy can yield the same strength enhancing advantagesdescribed hereinabove. This variation of the invention can beaccomplished by utilizing known methods to manufacture isocyanateterminated prepolymers from the epoxide CO₂ copolymeric polyols andadding these isocyanate-terminated materials to the A-side component ofthe foam formulation in place of a portion of the polyisocyanate used ina non-strengthened reference formulation. Methods of converting polyolsto isocyanate-terminated prepolymers by reacting the polyol with a molarexcess of a diisocyanate are well known in the art.

In certain embodiments, methods of the present invention include thestep of providing in the polyisocyanate component of a polyurethane foamcomposition, a strength enhancing additive comprising anisocyanate-terminated aliphatic polycarbonate polyol derived from thecopolymerization of CO₂ and one or more epoxides. Therefore, theinvention encompasses all of the variations and embodiments describedabove for the production of high strength polyurethane foamcompositions, but modified in that the step of strengthening the foamcomprises the sub-steps of:

-   -   a) reacting a polycarbonate polyol comprising a copolymer of CO₂        and one or more epoxides with an excess of a polyisocyanate (or        a reactive equivalent thereof), to provide an isocyanate        terminated polycarbonate polyol, and    -   b) adding the isocyanate terminated polycarbonate polyol to the        isocyanate component of a foam composition.

Further variations of the methods described above including theadditional steps necessary to formulate a finished foam will be readilyapparent to the skilled artisan. Therefore, while the presentspecification does not describe them, methods including additional stepstypical of foam formulation are specifically encompassed by the presentinvention. Such additional steps may include, but are not limited to:

-   -   addition of additional components to the A- and/or B-side        formulations (e.g. catalysts, blowing agents, pigments,        stabilizers, flame retardants, cell openers, surfactants,        reactive diluents, antimicrobials, and the like);    -   heating, cooling, mixing or combining the A-side and B-side        components; and    -   molding, extruding, blowing, spraying, heating, curing, aging,        or otherwise treating the foam formulation;

II. HIGH STRENGTH POLYURETHANE FOAM COMPOSITIONS

In another aspect, the present invention encompasses high strengthpolyurethane foam compositions. In certain embodiments, the inventivecompositions possess unexpected combinations of characteristicsincluding enhanced strength at a given density, or higher compressionforce deflection in combination with good comfort characteristics. Thesefoam compositions satisfy and an unmet need in the foam industry and itis anticipated that the compositions will have great value inapplications where high strength or good wearing properties mustcurrently be weighed against a desire for low density or low cost foams.

In certain embodiments, the present invention provides a polyurethanefoam composition comprising the reaction product of a polyol componentand a polyisocyanate component, where the polyol component comprises apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide. In certain embodiments, the polycarbonatepolyol is present in a quantity from about 1 weight percent to about 50weight percent of all polyols present in the polyol component. Incertain embodiments, the foam compositions are characterized in thattheir load bearing properties are higher than corresponding foamsformulated without the polycarbonate polyol.

In certain embodiments, foam compositions of the present inventioncomprise the reaction product of a polyol component and a polyisocyanatecomponent, where the polyol component contains a polycarbonate polyolderived from the copolymerization of one or more epoxides and carbondioxide. In certain embodiments, the polycarbonate polyol is present ina quantity from about 1 weight percent to about 50 weight percent of allpolyols present in the polyol component of the foam formulation. Incertain embodiments, the polycarbonate polyol is present in a quantityfrom about 2 weight percent to about 50 weight percent of all polyolspresent in the polyol component of the foam formulation. In certainembodiments, the polycarbonate polyol is present in a quantity fromabout 5 weight percent, to about 25 weight percent of all polyol presentin the polyol component. In certain embodiments, the polycarbonatepolyol is present in a quantity from about 1 weight percent to about 2weight percent of all polyol present in the polyol component. In certainembodiments, the polycarbonate polyol is present in a quantity fromabout 2 weight percent to about 5 weight percent of all polyol presentin the polyol component. In certain embodiments, the polycarbonatepolyol is present in a quantity from about 2 weight percent to about 10weight percent of all polyol present in the polyol component. In certainembodiments, the polycarbonate polyol is present in a quantity fromabout 5 weight percent to about 10 weight percent of all polyol presentin the polyol component. In certain embodiments, the polycarbonatepolyol is present in a quantity from about 10 weight percent, to about20 weight percent of all polyol present in the polyol component. Incertain embodiments, the polycarbonate polyol is present in a quantityfrom about 20 weight percent, to about 30 weight percent of all polyolpresent in the polyol component. In certain embodiments, thepolycarbonate polyol is present in a quantity from about 30 weightpercent, to about 50 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the polycarbonate polyol is presentin a quantity of about 1 weight percent of all polyol present in thepolyol component. In certain embodiments, the polycarbonate polyol ispresent in a quantity of about 1 weight percent of all polyol present inthe polyol component. In certain embodiments, the polycarbonate polyolis present in a quantity of about 2 weight percent of all polyol presentin the polyol component. In certain embodiments, the polycarbonatepolyol is present in a quantity of about 3 weight percent of all polyolpresent in the polyol component. In certain embodiments, thepolycarbonate polyol is present in a quantity of about 5 weight percentof all polyol present in the polyol component. In certain embodiments,the polycarbonate polyol is present in a quantity of about 10 weightpercent of all polyol present in the polyol component. In certainembodiments, the polycarbonate polyol is present in a quantity of about15 weight percent of all polyol present in the polyol component. Incertain embodiments, the polycarbonate polyol is present in a quantityof about 20 weight percent of all polyol present in the polyolcomponent. In certain embodiments, the polycarbonate polyol is presentin a quantity of about 25 weight percent of all polyol present in thepolyol component. In certain embodiments, the polycarbonate polyol ispresent in a quantity of about 30 weight percent of all polyol presentin the polyol component. In certain embodiments, the polycarbonatepolyol is present in a quantity of about 40 weight percent of all polyolpresent in the polyol component. In certain embodiments, thepolycarbonate polyol is present in a quantity of about 50 weight percentof all polyol present in the polyol component.

In certain embodiments, the other polyols present in the polyolcomponent (i.e. the polyols other than the polycarbonate polyol derivedfrom the copolymerization of one or more epoxides and carbon dioxide)are selected from the group consisting of: polyether polyols, polyesterpolyols, polybutadiene polyols, polysulfide polyols, natural oilpolyols, fluorinated polyols, aliphatic polyols, polycarbonate polyolsother than those derived from epoxide-CO₂ copolymerization, and mixturesof any two or more these. In certain embodiments, between about 50percent and about 99 percent of the total weight of polyol present inthe polyol component (i.e. exclusive of any other non-polyol componentsthat may be present in a B-side composition for foams such as catalysts,cell openers, blowing agents, stabilizers, diluents and the like)comprises one or more polyols selected from the group consisting ofpolyether polyols, polyester polyols, polybutadiene polyols, polysulfidepolyols, natural oil polyols, fluorinated polyols, aliphatic polyols,polycarbonate polyols other than those derived from epoxide-CO₂copolymerization and mixtures of any two or more these. In certainembodiments, the other polyol present in the polyol componentsubstantially comprises polyether polyol. In certain embodiments, theother polyol present in the polyol component substantially comprisespolyester polyol. In certain embodiments, the other polyols present inthe polyol component substantially comprise a mixture of polyether andpolyester polyols.

In certain embodiments, a high strength foam composition of the presentinvention comprises a polyol having a primary repeating unit having astructure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

In certain embodiments, a high strength foam composition of the presentinvention comprises a polyol having a primary repeating unit having astructure:

where R¹ is as defined above.

In certain embodiments, a high strength foam composition of the presentinvention comprises a polyol having a primary repeating unit having astructure:

wherein R¹ is, at each occurrence in the polymer chain, independently—H, or —CH₃.

In certain embodiments, the high strength foam compositions describedabove are characterized in that the polycarbonate polyol derived fromthe copolymerization of one or more epoxides and carbon dioxide has anumber average molecular weight (Mn) between about 500 g/mol and about20,000 g/mol. In certain embodiments, the polycarbonate polyol has an Mnbetween about 1,000 g/mol and about 5,000 g/mol. In certain embodiments,the polycarbonate polyol has an Mn between about 1,000 g/mol and about3,000 g/mol. In certain embodiments, the polycarbonate polyol has an Mnof about 1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000g/mol, about 2,500 g/mol or about 3,000 g/mol.

In certain embodiments, the high strength foam compositions describedabove are characterized in that the polycarbonate polyol incorporated asan additive has a high percentage of end groups reactive towardisocyanates. In certain embodiments, more than 98%, more than 99%, morethan 99.5%, more than 99.8%, more than 99.9%, or essentially 100% of thepolycarbonate polyol chain ends are groups reactive toward isocyanates.In certain embodiments, the chain ends reactive toward isocyanatescomprise —OH groups.

In certain embodiments, the high strength foam compositions describedabove are characterized in that the polycarbonate polyols incorporatedas additives are substantially compatible with or soluble in otherpolyols present in the polyol component of the foam formulations.Substantially compatible in this context means that the aliphaticpolycarbonate can be mixed with the other polyol or polyols and providea mixture that is homogenous or nearly homogenous. In certainembodiments, the mixture is largely homogenous at ambient temperaturewhile in other embodiments, the mixture is homogenous at elevatedtemperatures (for example the mixture is homogenous at 30° C., at 40°C., at 80° C., at 100° C. or at 140° C.). In certain embodiments, thepolyol component of the foam formulation containing the aliphaticpolycarbonate polyol is a substantially homogenous transparent mixture.

In certain embodiments, the high strength foam compositions of thepresent invention are characterized in that the structure of thealiphatic polycarbonate polyol incorporated is chosen to enhance itscompatibility with other polyols in the polyol component of the foamformulation. In certain embodiments, the aliphatic polycarbonate polyolis characterized in that it has one or more ether linkages present in achain transfer agent embedded within the polycarbonate chain. In certainembodiments, such ether linkages derive from the use of diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols, orpolyethylene-co-propylene glycols as chain transfer agents in thepreparation of the aliphatic polycarbonate polyol. In certainembodiments, such ether linkages are provided by utilizing ethoxylatedor propolxylated diols, triols, or higher polyhydric alcohols havingfour or more —OH groups. In certain embodiments, such ether linkages areprovided by utilizing isosorbide, or other carbohydrate-derivedmaterials as chain transfer agents.

In certain embodiments, the high strength foam compositions of thepresent invention are characterized in that the aliphatic polycarbonatepolyol used in the compositions has a functional number of 2 or about 2.In certain embodiments the aliphatic polycarbonate polyols have afunctional number greater than 2. In certain embodiments the aliphaticpolycarbonate polyols have a functional number between 2 and 4. Incertain embodiments the aliphatic polycarbonate polyols have afunctional number between 2 and 3. In certain embodiments the aliphaticpolycarbonate polyols have a functional number between 2 and about 2.6,between 2 and about 2.5, or between 2 and about 2.4. In certainembodiments, the aliphatic polycarbonate polyol is characterized in thatit comprises a mixture of diol (functional number 2) with one or morehigher functional polyols (e.g. a polyol with a functional number of 3,4, 5, or 6).

In certain embodiments, the high strength foam compositions of thepresent invention are characterized in that they incorporate analiphatic polycarbonate polyol having a number average molecular weight(Mn) less than about 10,000 g/mol. In certain embodiments, theincorporated aliphatic polycarbonate polyols have Mn between 400 andabout 10,000 g/mol. In certain embodiments, the incorporated aliphaticpolycarbonate polyols are characterized in that they have an Mn between400 and about 5,000 g/mol, between 500 and about 3,000 g/mol, between700 and about 2,500 g/mol, between 1,000 and 3,000 g/mol, or between 700and 1500 g/mol.

In certain embodiments, the high strength foam compositions of thepresent invention are characterized in that they incorporate a copolymerof carbon dioxide and one or both of ethylene oxide and propylene oxidehaving an Mn less than 10,000 g/mol, a functional number between 2 and4, and having one or more ether linkages present in a chain transferagent embedded within the polycarbonate chain. In certain embodiments,the incorporated polycarbonate polyol comprises poly(propylenecarbonate) containing an embedded chain transfer agent derived fromdiethylene glycol, dipropylene glycol, triethylene glycol, tripropyleneglycol, higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 5,000 g/mol, and afunctional number between 2 and 3. In certain embodiments, theincorporated polycarbonate polyol comprises poly(propylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 3,000 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, theincorporated polycarbonate polyol comprises poly(propylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn between 500 and 2,500 g/mol, and afunctional number between 2 and 2.5.

In certain embodiments, the incorporated polycarbonate polyol comprisespoly(ethylene carbonate) containing an embedded chain transfer agentderived from diethylene glycol, dipropylene glycol, triethylene glycol,tripropylene glycol, higher polyethylene glycols, higher polypropyleneglycols, polyethylene-co-propylene glycols, or alkoxylated polyhydricalcohols, characterized in that it has an Mn less than 5,000 g/mol, anda functional number between 2 and 3. In certain embodiments, theincorporated polycarbonate polyol comprises poly(ethylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn less than 3,000 g/mol, and afunctional number between 2 and 2.5. In certain embodiments, theincorporated polycarbonate polyol comprises poly(ethylene carbonate)containing an embedded chain transfer agent derived from diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol,higher polyethylene glycols, higher polypropylene glycols,polyethylene-co-propylene glycols, or alkoxylated polyhydric alcohols,characterized in that it has an Mn between 500 and 2,500 g/mol, and afunctional number between 2 and 2.5.

In certain embodiments, a provided polycarbonate polyol comprisespoly(ethylene-co-propylene carbonate) containing an embedded chaintransfer agent derived from diethylene glycol, dipropylene glycol,triethylene glycol, tripropylene glycol, higher polyethylene glycols,higher polypropylene glycols, polyethylene-co-propylene glycols, oralkoxylated polyhydric alcohols, characterized in that it has an Mn lessthan 5,000 g/mol, and a functional number between 2 and 3. In certainembodiments, the incorporated polycarbonate polyol comprisespoly(ethylene-co-propylene carbonate) containing an embedded chaintransfer agent derived from diethylene glycol, dipropylene glycol,triethylene glycol, tripropylene glycol, higher polyethylene glycols,higher polypropylene glycols, polyethylene-co-propylene glycols, oralkoxylated polyhydric alcohols, characterized in that it has an Mn lessthan 3,000 g/mol, and a functional number between 2 and 2.5. In certainembodiments, the incorporated polycarbonate polyol comprisespoly(ethylene-co-propylene carbonate) containing an embedded chaintransfer agent derived from diethylene glycol, dipropylene glycol,triethylene glycol, tripropylene glycol, higher polyethylene glycols,higher polypropylene glycols, polyethylene-co-propylene glycols, oralkoxylated polyhydric alcohols, characterized in that it has an Mnbetween 500 and 2,500 g/mol, and a functional number between 2 and 2.5.

The structures and properties of aliphatic polycarbonate polyols thatmay be incorporated in the high strength foam compositions of thepresent invention are more fully described in Appendix A at the end ofthis specification entitled “Aliphatic Polycarbonate Polyols”. Incertain embodiments, the present invention encompasses any of the foamformulations described above, wherein the polycarbonate polyol used intheir formulation is selected from any one or more of those described inAppendix A.

High strength foam compositions of the present invention comprise thereaction product of any of the B-side mixtures containing aliphaticpolycarbonate polyols described above with an A-side formulationcomprising one or more polyisocyanates. In certain embodiments, the highstrength foam compositions of the present invention comprise MDI-basedpolyurethane foams. In certain embodiments, the high strength foamcompositions of the present invention comprise TDI-based polyurethanefoams.

The art of polyurethane synthesis is well advanced and a very largenumber of isocyanates and related polyurethane precursors are known inthe art and available commercially. It is to be understood that it iswithin the capabilities of one skilled in the art of polyurethaneformulation to select and use such isocyanates along with the teachingsof this disclosure to produce high strength foams within the scope ofthe present invention. Descriptions of suitable isocyanate compounds andanalogs can be found in: Chemistry and Technology of Polyols forPolvurethanes Ionescu, Mihail 2005 (ISBN 978-1-84735-035-0), and H.Ulrich, “Urethane Polymers,” Kirk-Othmer Encyclopedia of ChemicalTechnology, 1997 the entirety of each of which is incorporated herein byreference. In certain embodiments, the inventive foams comprise thereaction product of any of the polyol formulations described above withA-side formulations containing one or more of the isocyanate reagentsdescribed in Appendix B entitled Isocyanate Reagents appearing at theend of this specification.

In certain embodiments, a high strength foam composition of the presentinvention comprises a flexible polyurethane foam. In certainembodiments, a high strength foam composition of the present inventioncomprises a viscoelastic polyurethane foam. In certain embodiments, ahigh strength foam composition of the present invention comprises arigid polyurethane foam.

In certain embodiments, the inventive high strength foams describedabove comprise flexible foam compositions. In certain embodiments, theinventive high strength foams described above high resilience flexiblefoam compositions. In certain embodiments, the present inventionprovides articles manufactured from such flexible foam compositions.Such articles include, but are not limited to: slabstock foams, seatingcushions for residential and office use, mattresses, personal protectivegear, athletic equipment, office furniture, transportation seating,automotive interior components and surfaces such as dash boards, doorpanels, headliners and the like.

A. Flexible Foam Compositions

In certain embodiments, compositions of the present invention comprisehigh strength flexible polyurethane foam compositions derived from aB-side composition comprising a polyether polyol in combination with apolycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide. In certain embodiments the polycarbonatepolyol is present in such a quantity that the final B-side compositioncontains from about 1 part to about 100 parts by weight of polycarbonatepolyol based on 100 parts of polyether polyol. In certain embodiments,the polycarbonate polyol is present in such a quantity that thepolycarbonate polyol comprises about 5 parts, about 10 parts, about 20parts, about 30 parts, about 40 parts, about 60 parts, about 80 parts,or about 100 parts, based on 100 parts of polyether polyol in theresulting B-side formulation. In certain embodiments, the aliphaticpolycarbonate polyol comprises poly(propylene carbonate). In certainembodiments, the aliphatic polycarbonate polyol present comprisespoly(ethylene carbonate). In certain embodiments, the aliphaticpolycarbonate polyol present comprises poly(ethylene-co-propylenecarbonate).

In certain embodiments, high strength flexible foam compositions of thepresent invention are characterized in that foams have higher strengththan corresponding foams formulated without the polycarbonate polyol. Incertain embodiments, the inventive foams are characterized in that oneor more properties selected from the group consisting of: TensileStrength at Break (as measured by ASTM D3574-08 Test E); Tear Strength(as measured by ASTM D3574-08 Test F); Compression Force Deflection(CFD) (as measured by ASTM D3574-08 Test C); and Tensile strength andElongation after Dry Heat Aging for 22 hours at 140° C. (as measured byASTM D3574-08Test K) are enhanced relative to those of a correspondingreference foam formulated without the polycarbonate polyol additive.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions (denoted the strengthened foamformulation) comprising a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide andcharacterized in that the load bearing capacity of the strengthened foamas indicated by its compression force deflection (CFD) value measuredusing ASTM D3574-08 Test C, is greater than the CFD value of thecorresponding foam composition formulated without the addedpolycarbonate polyol (denoted the reference foam formulation). Incertain embodiments, the aliphatic polycarbonate polyol is present inthe B-side formulation in place of a portion of one or more polyols inthe reference. Preferably, this is achieved such that the —OH number ofthe B-side formulation for the strengthened foam is substantially thesame as that of the B-side formulation of the reference foamformulation. In certain embodiments, the inventive high strength foam ischaracterized in that the CFD value of the strengthened foam is at least10% greater than the CFD value of the reference foam formulation. Incertain embodiments, the high strength foam is characterized in that theCFD value of the strengthened foam is at least 10% greater, at least 20%greater, at least 30% greater, at least 40% greater, at least 50%greater, or at least 100% greater than the CFD value of the referencefoam. In certain embodiments, the CFD values of the strengthened foamand the reference foam are normalized for the density of the foam priorto comparing them. In certain embodiments foam compositions of thepresent invention are characterized in that they have substantially thesame density as the reference foam composition to which they arecompared.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions (denoted the strengthened foamformulation) containing an additive comprising a polycarbonate polyolderived from the copolymerization of one or more epoxides and carbondioxide and characterized in that the strengthened foam formulation hasa lower density than the corresponding foam composition formulatedwithout the additive (denoted the reference foam formulation) furthercharacterized in that the load bearing properties (CFD) of thestrengthened foam as determined by ASTM D3574-08 Test C, are equal to orgreater than those of the reference foam. In certain embodiments, thecomposition is characterized in that the additive is provided in theB-side formulation from which the foam is produced by substituting aportion of one or more polyols in the reference formulation such thatthe —OH number of the B-side formulation for the strengthened foam issubstantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the inventivepolyurethane foam composition is characterized in that the density ofthe strengthened foam formulation is at least 10% lower than the densityof the reference foam formulation. In certain embodiments, the inventivestrength polyurethane foam composition is characterized in that thedensity of the strengthened foam formulation is at least 10%, at least20%, at least 30%, at least 40%, or at least 50%, less than the densityof the reference foam. In certain embodiments, the inventive foamcomposition is characterized in that its density is at least 10%, atleast 20%, at least 30%, at least 40%, or at least 50%, less than thedensity of the reference foam while the CFD of the strengthened foam isat least equal to, at least 10% greater than, at least 20% greater than,at least 30% greater than, at least 40% greater than, at least 50%greater than, at least 75% greater than, or at least 100% greater thanthe CFD of the reference foam.

In certain embodiments, the present invention provides high strengthflexible TDI-based polyurethane foam compositions having the combinationof a density of less than about 2.6 pounds/cubic foot (pcf) and a CFD asmeasured by ASTM D3574-08 Test C of at least 0.4 psi at 25% deflection.In certain embodiments, the method is characterized in that the CFDvalue is at least 0.45 psi at 25% deflection, at least 0.5 psi at 25%deflection, or at least 0.52 psi at 25% deflection. In certainembodiments, the high strength flexible TDI-based polyurethane foam ischaracterized in that the CFD value of the foam measured by ASTMD3574-08 Test C is at least 0.5 psi at 50% deflection. In certainembodiments, high strength flexible TDI-based polyurethane foam ischaracterized in that the CFD value of the strengthened foam measured byASTM D3574-08 Test C is at least 0.55 psi at 50% deflection, at least0.60 psi at 50% deflection, at least 0.65 psi at 50% deflection, atleast 0.7 psi at 50% deflection, or at least 0.75 psi at 50% deflection.In certain embodiments, the high strength flexible TDI-basedpolyurethane foam is characterized in that the CFD value of the foammeasured by ASTM D3574-08 Test C is at least 0.7 psi at 65% deflection.In certain embodiments, high strength flexible TDI-based polyurethanefoam is characterized in that the CFD value of the strengthened foammeasured by ASTM D3574-08 Test C is at least 0.75 psi at 65% deflection,at least 0.80 psi at 65% deflection, at least 0.85 psi at 65%deflection, at least 0.9 psi at 65% deflection, or at least 1 psi at 65%deflection. In certain embodiments, the CFD values above are for a foamcomposition having a density of between about 2 and 2.6 pcf. In certainembodiments, the high strength flexible TDI-based polyurethane foam hasa density of between about 2.2 and 2.6 pcf, or a density of about 2.4pcf. In certain embodiments, the high strength flexible TDI-basedpolyurethane foam has a density between about 2 and 2.6 pcf and isfurther characterized in that it contains less than 10% filled polyol,less than 5% filled polyol, less than 3% filled polyol, less than 2%filled polyol, less than 1% filled polyol, or characterized in that itis substantially free of filled polyol. In certain embodiments, the foamformulations above are characterized in that they have comfortproperties suitable for use in seating foams.

In certain embodiments, the present invention provides high strengthflexible TDI-based polyurethane foam compositions having the combinationof a density of less than about 4 pcf and a CFD as measured by ASTMD3574-08 Test C of at least 0.8 psi at 25% deflection. In certainembodiments, the method is characterized in that the CFD value of thestrengthened foam formulation is at least 0.85 psi at 25% deflection, atleast 0.9 psi at 25% deflection, at least 0.95 psi at 25% deflection, orat least 1 psi at 25% deflection. In certain embodiments, the method ischaracterized in that the CFD value of the strengthened foam with adensity of less than about 4 pcf as measured by ASTM D3574-08 Test C isat least 1 psi at 50% deflection. In certain embodiments, the highstrength foam composition is characterized in that its CFD value is atleast 1.1 psi at 50% deflection, at least 1.15 psi at 50% deflection, atleast 1.2 psi at 50% deflection, at least 1.3 psi at 50% deflection, orat least 1.4 psi at 50% deflection.

In certain embodiments, the high strength TDI-based foam composition ischaracterized in that the foam has a combination of a density of lessthan about 4 pcf and a CFD as measured by ASTM D3574-08 Test C of atleast 1.4 psi at 65% deflection. In certain embodiments, the highstrength foam composition is characterized in that the CFD value of thefoam is at least 1.5 psi at 65% deflection, at least 1.6 psi at 65%deflection, at least 1.7 psi at 65% deflection, at least 1.8 psi at 65%deflection, at least 1.9 psi at 65% deflection, or at least 2 psi at 65%deflection. In certain embodiments, the high strength TDI-based foamcomposition has a density of between about 3.2 and 3.8 pcf. In certainembodiments, the high strength TDI-based foam composition has a densityof between about 3.3 and 3.7 pcf, or a density of about 3.5 pcf. Incertain embodiments, the high strength TDI-based foam composition has adensity between about 3.2 and 3.8 pcf and is further characterized inthat it contains less than 10% filled polyol, less than 5% filledpolyol, less than 3% filled polyol, less than 2% filled polyol, lessthan 1% filled polyol, or characterized in that it is substantially freeof filled polyol. In certain embodiments, the foam formulations aboveare characterized in that they have comfort properties suitable for usein seating foams.

In certain embodiments, the present invention provides high strengthflexible MDI-based polyurethane foam compositions having the combinationof a density of less than about 2.5 pounds/cubic foot (pcf) and a CFD asmeasured by ASTM D3574-08 Test C of at least 0.35 psi at 25% deflection.In certain embodiments, the method is characterized in that the CFDvalue is at least 0.4 psi at 25% deflection, at least 0.45 psi at 25%deflection, or at least 0.5 psi at 25% deflection. In certainembodiments, the high strength flexible MDI-based polyurethane foam ischaracterized in that the CFD value of the foam measured by ASTMD3574-08 Test C is at least 0.4 psi at 50% deflection. In certainembodiments, high strength flexible MDI-based polyurethane foam ischaracterized in that the CFD value of the strengthened foam measured byASTM D3574-08 Test C is at least 0.45 psi at 50% deflection, at least0.50 psi at 50% deflection, at least 0.55 psi at 50% deflection, atleast 0.6 psi at 50% deflection, or at least 0.65 psi at 50% deflection.In certain embodiments, the high strength flexible MDI-basedpolyurethane foam is characterized in that the CFD value of the foammeasured by ASTM D3574-08 Test C is at least 0.7 psi at 65% deflection.In certain embodiments, high strength flexible MDI-based polyurethanefoam is characterized in that the CFD value of the strengthened foammeasured by ASTM D3574-08 Test C is at least 0.75 psi at 65% deflection,at least 0.80 psi at 65% deflection, at least 0.85 psi at 65%deflection, at least 0.9 psi at 65% deflection, or at least 1 psi at 65%deflection. In certain embodiments, the high strength MDI-based foamshave a density of between about 2 and 2.6 pcf. In certain embodimentsthe high strength MDI-based foams have a density of between about 2.2and 2.6 pcf, or a density of about 2.4 pcf. In certain embodiments, thehigh strength MDI-based foams have a density between about 2 and 2.6 pcfand are further characterized in that they contain less than 10% filledpolyol, less than 5% filled polyol, less than 3% filled polyol, lessthan 2% filled polyol, less than 1% filled polyol, or are characterizedin that they are substantially free of filled polyol. In certainembodiments, the foam formulations above are characterized in that theyhave comfort properties suitable for use in seating foams.

In certain embodiments, the present invention provides high strengthflexible MDI-based polyurethane foam compositions having the combinationof a density of less than about 4 pcf and a CFD as measured by ASTMD3574-08 Test C of at least 0.8 psi at 25% deflection. In certainembodiments, the method is characterized in that the CFD value of thestrengthened foam formulation is at least 0.85 psi at 25% deflection, atleast 0.9 psi at 25% deflection, at least 0.95 psi at 25% deflection, orat least 1 psi at 25% deflection. In certain embodiments, the method ischaracterized in that the CFD value of the strengthened foam with adensity of less than about 4 pcf as measured by ASTM D3574-08 Test C isat least 1 psi at 50% deflection. In certain embodiments, the highstrength foam composition is characterized in that its CFD value is atleast 1.1 psi at 50% deflection, at least 1.2 psi at 50% deflection, atleast 1.4 psi at 50% deflection, at least 1.5 psi at 50% deflection, orat least 1.8 psi at 50% deflection.

In certain embodiments, the high strength MDI-based foam composition ischaracterized in that the foam has a combination of a density of lessthan about 4 pcf and a CFD as measured by ASTM D3574-08 Test C of atleast 1.4 psi at 65% deflection. In certain embodiments, the highstrength foam composition is characterized in that the CFD value of thefoam is at least 1.5 psi at 65% deflection, at least 1.6 psi at 65%deflection, at least 1.7 psi at 65% deflection, at least 1.8 psi at 65%deflection, at least 1.9 psi at 65% deflection, at least 2 psi at 65%deflection, or at least 3 psi at 65% deflection. In certain embodiments,the high strength MDI-based foam composition has a density of betweenabout 3.2 and 3.8 pcf. In certain embodiments, the high strengthMDI-based foam composition has a density of between about 3.3 and 3.7pcf, or a density of about 3.5 pcf. In certain embodiments, the highstrength MDI-based foam composition has a density between about 3.2 and3.8 pcf and is further characterized in that it contains less than 10%filled polyol, less than 5% filled polyol, less than 3% filled polyol,less than 2% filled polyol, less than 1% filled polyol, or characterizedin that it is substantially free of filled polyol. In certainembodiments, the foam formulations above are characterized in that theyhave comfort properties suitable for use in seating foams.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions (denoted the strengthened foamformulation) containing an additive comprising a polycarbonate polyolderived from the copolymerization of one or more epoxides and carbondioxide, and characterized in that the tensile strength of thestrengthened foam as measured by ASTM D 3574-08 Test E, is greater thanthe tensile strength of a corresponding foam composition formulatedwithout the added polycarbonate polyol (denoted the reference foamformulation). In certain embodiments, the aliphatic polycarbonate polyolis present in the B-side formulation in place of a portion of one ormore polyols in the reference. Preferably, this is achieved such thatthe —OH number of the B-side formulation for the strengthened foam issubstantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the inventive highstrength foam is characterized in that the tensile strength of thestrengthened foam is at least 10% greater than the tensile strength ofthe reference foam formulation. In certain embodiments, the highstrength foam is characterized in that the tensile strength of thestrengthened foam is at least 10% greater, at least 20% greater, atleast 30% greater, at least 40% greater, at least 50% greater, or atleast 100% greater than the tensile strength of the reference foam. Incertain embodiments, the tensile strengths of the strengthened foam andthe reference foam are normalized for the density of the foam prior tocomparing them. In certain embodiments foam compositions of the presentinvention are characterized in that they have substantially the samedensity as the reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions containing an additivecomprising a polycarbonate polyol derived from the copolymerization ofone or more epoxides and carbon dioxide. In certain embodiments, theinventive foam compositions are characterized in that they have a lowerdensity than a corresponding foam composition formulated without thepolycarbonate polyol additive (denoted the reference foam formulation)and further characterized in that the tensile strength of thestrengthened foam as determined by ASTM D3574-08 Test E is equal to orgreater than that of the reference foam. In certain embodiments, thecomposition is characterized in that the additive is provided in theB-side formulation from which the foam is produced by substituting aportion of one or more polyols in the reference formulation such thatthe —OH number of the B-side formulation for the strengthened foam issubstantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the inventivepolyurethane foam composition is characterized in that the density ofthe strengthened foam formulation is at least 10% lower than the densityof the reference foam formulation. In certain embodiments, the inventivestrength polyurethane foam composition is characterized in that thedensity of the strengthened foam formulation is at least 10%, at least20%, at least 30%, at least 40%, or at least 50%, less than the densityof the reference foam. In certain embodiments, the inventive foamcomposition is characterized in that its density is at least 10%, atleast 20%, at least 30%, at least 40%, or at least 50%, less than thedensity of the reference foam while the tensile strength of thestrengthened foam is at least equal to, at least 10% greater than, atleast 20% greater than, at least 30% greater than, at least 40% greaterthan, at least 50% greater than, at least 75% greater than, or at least100% greater than the tensile strength of the reference foam.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions (denoted the strengthened foamformulation) containing an additive comprising a polycarbonate polyolderived from the copolymerization of one or more epoxides and carbondioxide, and characterized in that the tear strength of the strengthenedfoam as measured by ASTM D 3574-08 Test E, is greater than the tensilestrength of a corresponding foam composition formulated without theadded polycarbonate polyol (denoted the reference foam formulation). Incertain embodiments, the aliphatic polycarbonate polyol is present inthe B-side formulation in place of a portion of one or more polyols inthe reference. Preferably, this is achieved such that the —OH number ofthe B-side formulation for the strengthened foam is substantially thesame as that of the B-side formulation of the reference foamformulation. In certain embodiments, the inventive high strength foam ischaracterized in that the tensile strength of the strengthened foam isat least 10% greater than the tensile strength of the reference foamformulation. In certain embodiments, the high strength foam ischaracterized in that the tensile strength of the strengthened foam isat least 10% greater, at least 20% greater, at least 30% greater, atleast 40% greater, at least 50% greater, or at least 100% greater thanthe tensile strength of the reference foam. In certain embodiments, thetensile strengths of the strengthened foam and the reference foam arenormalized for the density of the foam prior to comparing them. Incertain embodiments foam compositions of the present invention arecharacterized in that they have substantially the same density as thereference foam composition to which they are compared.

In certain embodiments, the present invention provides high strengthflexible polyurethane foam compositions containing an additivecomprising a polycarbonate polyol derived from the copolymerization ofone or more epoxides and carbon dioxide. In certain embodiments, theinventive foam compositions are characterized in that they have a lowerdensity than a corresponding foam composition formulated without thepolycarbonate polyol additive (denoted the reference foam formulation)and further characterized in that the tear strength of the strengthenedfoam as determined by ASTM D 3574-08 Test F is equal to or greater thanthat of the reference foam. In certain embodiments, the composition ischaracterized in that the additive is provided in the B-side formulationfrom which the foam is produced by substituting a portion of one or morepolyols in the reference formulation such that the —OH number of theB-side formulation for the strengthened foam is substantially the sameas that of the B-side formulation of the reference foam formulation. Incertain embodiments, the inventive polyurethane foam composition ischaracterized in that the density of the strengthened foam formulationis at least 10% lower than the density of the reference foamformulation. In certain embodiments, the inventive strength polyurethanefoam composition is characterized in that the density of thestrengthened foam formulation is at least 10%, at least 20%, at least30%, at least 40%, or at least 50%, less than the density of thereference foam. In certain embodiments, the inventive foam compositionis characterized in that its density is at least 10%, at least 20%, atleast 30%, at least 40%, or at least 50%, less than the density of thereference foam while the tear strength of the strengthened foam is atleast equal to, at least 10% greater than, at least 20% greater than, atleast 30% greater than, at least 40% greater than, at least 50% greaterthan, at least 75% greater than, or at least 100% greater than thetensile strength of the reference foam.

B. Viscoelastic Foam Compositions

Viscoelastic (VE) foams are typically water blown foams produced using amixture of low molecular weight hydrophobic polyols, high molecularweight polyols produced from propylene oxide and ethylene oxide andshort molecular weight chain extenders. These foams are usually producedat relatively low isocyanate indexes which facilitate an open cellstructure. In order to balance foaming rate and open cell morphology,polyols with high levels of hydrophilic oxyethylene groups are used inpreparation of these foams as well as a variety of surfactants. In orderto produce soft (compliant) foams, isocyanates such as TDI or mixturesof 4,4′- and 2,4′-MDI are typically used in production of VE foams.Calcium carbonate or other fillers can also be added to theseformulations to increase density (and load bearing properties) and toreduce tackiness.

In certain embodiments, the present invention provides novel VE foamscharacterized in that at least a portion of one or more of the polyolsin the B-side formulation is replaced with a polycarbonate polyolderived from copolymerization of CO₂ and one or more epoxides. Incertain embodiments, the VE foam compositions are further characterizedin that they contain less or no inorganic filler than a comparative foamhaving similar viscoelastic properties but lacking the polycarbonatepolyol additive. In certain embodiments the polycarbonate polyol ispresent in such a quantity that the final B-side composition containsfrom about 1 part to about 100 parts by weight of polycarbonate polyolbased on 100 parts of polyether polyol. In certain embodiments, thepolycarbonate polyol is present in such a quantity that thepolycarbonate polyol comprises about 5 parts, about 10 parts, about 20parts, about 30 parts, about 40 parts, about 60 parts, about 80 parts,or about 100 parts, based on 100 parts of polyether polyol in theresulting B-side formulation. In certain embodiments, the aliphaticpolycarbonate polyol comprises poly(propylene carbonate). In certainembodiments, the aliphatic polycarbonate polyol present comprisespoly(ethylene carbonate). In certain embodiments, the aliphaticpolycarbonate polyol present comprises poly(ethylene-co-propylenecarbonate).

In certain embodiments, high strength VE foam compositions of thepresent invention are characterized in that foams have higher strengththan corresponding foams formulated without the polycarbonate polyoladditive. In certain embodiments, the inventive foams are characterizedin that one or more properties selected from the group consisting of:Tensile Strength at Break (as measured by ASTM D3574-08 Test E); TearStrength (as measured by ASTM D3574-08 Test F); Compression ForceDeflection (CFD) (as measured by ASTM D3574-08 Test C); and Tensilestrength and Elongation after Dry Heat Aging for 22 hours at 140° C. (asmeasured by ASTM D3574-08Test K) are enhanced relative to those of acorresponding reference foam formulated without the polycarbonate polyoladditive.

In certain embodiments, the present invention provides high strength VEfoam compositions (denoted the strengthened foam formulation) comprisinga polycarbonate polyol derived from the copolymerization of one or moreepoxides and carbon dioxide and characterized in that the load bearingcapacity of the strengthened foam as indicated by its compression forcedeflection (CFD) value measured using ASTM D3574-08 Test C, is greaterthan the CFD value of a corresponding VE foam composition formulatedwithout the added polycarbonate polyol (denoted the reference foamformulation). In certain embodiments, the aliphatic polycarbonate polyolis present in the B-side formulation in place of a portion of one ormore polyols in the reference foam. Preferably, this is achieved suchthat the —OH number of the B-side formulation for the strengthened foamis substantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the inventive highstrength foam is characterized in that the CFD value of the strengthenedfoam is at least 10% greater than the CFD value of the reference foamformulation. In certain embodiments, the high strength foam ischaracterized in that the CFD value of the strengthened foam is at least10% greater, at least 20% greater, at least 30% greater, at least 40%greater, at least 50% greater, or at least 100% greater than the CFDvalue of the reference foam. In certain embodiments, the CFD values ofthe strengthened foam and the reference foam are normalized for thedensity of the foam prior to comparing them. In certain embodiments foamcompositions of the present invention are characterized in that theyhave substantially the same density as the reference foam composition towhich they are compared.

In certain embodiments, the present invention provides high strength VEfoam compositions (denoted the strengthened foam formulation) containingan additive comprising a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide, andcharacterized in that the tensile strength of the strengthened foam asmeasured by ASTM D 3574-08 Test E, is greater than the tensile strengthof a corresponding foam composition formulated without the addedpolycarbonate polyol (denoted the reference foam formulation). Incertain embodiments, the aliphatic polycarbonate polyol is present inthe B-side formulation in place of a portion of one or more polyols inthe reference. Preferably, this is achieved such that the —OH number ofthe B-side formulation for the strengthened foam is substantially thesame as that of the B-side formulation of the reference foamformulation. In certain embodiments, the inventive high strength foam ischaracterized in that the tensile strength of the strengthened foam isat least 10% greater than the tensile strength of the reference foamformulation. In certain embodiments, the high strength foam ischaracterized in that the tensile strength of the strengthened foam isat least 10% greater, at least 20% greater, at least 30% greater, atleast 40% greater, at least 50% greater, or at least 100% greater thanthe tensile strength of the reference foam. In certain embodiments, thetensile strengths of the strengthened foam and the reference foam arenormalized for the density of the foam prior to comparing them. Incertain embodiments foam compositions of the present invention arecharacterized in that they have substantially the same density as thereference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength VEfoam compositions (denoted the strengthened foam formulation) containingan additive comprising a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide, andcharacterized in that the tear strength of the strengthened foam asmeasured by ASTM D 3574-08 Test E, is greater than the tensile strengthof a corresponding foam composition formulated without the addedpolycarbonate polyol (denoted the reference foam formulation). Incertain embodiments, the aliphatic polycarbonate polyol is present inthe B-side formulation in place of a portion of one or more polyols inthe reference foam. Preferably, this is achieved such that the —OHnumber of the B-side formulation for the strengthened foam issubstantially the same as that of the B-side formulation of thereference foam formulation. In certain embodiments, the inventive highstrength foam is characterized in that the tensile strength of thestrengthened foam is at least 10% greater than the tensile strength ofthe reference foam formulation. In certain embodiments, the highstrength foam is characterized in that the tensile strength of thestrengthened foam is at least 10% greater, at least 20% greater, atleast 30% greater, at least 40% greater, at least 50% greater, or atleast 100% greater than the tensile strength of the reference foam. Incertain embodiments, the tensile strengths of the strengthened foam andthe reference foam are normalized for the density of the foam prior tocomparing them. In certain embodiments foam compositions of the presentinvention are characterized in that they have substantially the samedensity as the reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength VEfoam compositions (denoted the strengthened foam formulation) containingan additive comprising a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide, andcharacterized in that the energy absorbing properties of the foam areincreased. In certain embodiments this increase in energy absorptionindicated by an increase in hysteresis loss according to ASTM 3574-08,Hysteresis Procedure B. In certain embodiments, the hysteresis loss isgreater in the inventive VE foam than that of a corresponding foamcomposition formulated without the added polycarbonate polyol (denotedthe reference foam formulation). In certain embodiments, the inventivehigh strength foam is characterized in that its hysteresis loss is atleast 10% greater than that of the reference foam formulation. Incertain embodiments, the inventive high strength foam is characterizedin that its hysteresis loss is at least 20% greater, at least 30%greater, at least 40% greater, at least 50% greater, or at least 100%greater than the hysteresis loss of the reference foam under identicalconditions.

In certain embodiments, viscoelastic foam compositions of the presentinvention are characterized in that they have a reduced quantity ofinorganic filler.

C. Foams with Novel Physical Properties

In another aspect, the present invention encompasses foam compositionshaving a novel combination of physical properties. In certainembodiments, the invention provides a flexible polyurethane foamcomprising the reaction product of a B-side mixture substantiallycomprising polyether polyol and an A-side mixture comprising one or moreof MDI or TDI characterized in that the foam has the combination of:

-   -   a density less than 40 kg/m³ by ASTM D 3574-08, Test A;    -   a CFD at 65% of greater than 1 psi (or 3 kPa) by ASTM D 3574-08,        Test C; and    -   a SAG factor of between 2.0 and 3.0 (obtained from ASTM D        3574-08, Test C by dividing the CFD @ 65% compression by the CFD        at 25% compression).

In certain embodiments, the inventive foam is characterized in that ithas the combination of: a density by ASTM D 3574-08, Test A, of lessthan 38, less than 36, less than 34, less than 32 or less than 30 kg/m³and a CFD by ASTM D 3574-08, Test C greater than 1.6 psi at 65% and aSAG factor of about 2.

In certain embodiments, the inventive foam is characterized in that ithas the combination of: A CFD at 65% by ASTM D 3574-08, Test C ofgreater than 0.8 psi, greater than 1.0 psi, greater than 1.2 psi,greater than 1.4 psi, or greater than 1.6 psi, greater than 1.8 psi, orgreater than 2 psi, with a density less than 40 kg/m³, and a comfortfactor between 2 and 3.

In certain embodiments, the inventive foam is characterized in that ithas the combination of: A CFD at 65% by ASTM D 3574-08, Test C ofgreater than 1 psi, greater than 1.2 psi, greater than 1.4 psi, greaterthan 1.5 psi, or greater than 1.75 psi, or greater than 2 psi; with adensity less than 38, less than 36, less than 34, less than 32 or lessthan 30 kg/m³ by ASTM D 3574-08, Test A, and a comfort factor between 2and 3.

One approach used in the field of polyurethane foams today to increasethe strength or CFD of flexible foams is the addition of graft polyolsto the B-side formulation. Graft polyols (also called filled polyols orpolymer polyols) contain finely dispersed styrene-acrylonitrile,acrylonitrile, or polyurea (PHD) polymer solids chemically grafted to apolyether backbone. They are used to increase the load-bearingproperties of low-density high-resiliency (HR) foam, as well as to addtoughness to microcellular foams and cast elastomers. However, thesematerials increase the cost of the foams and sometimes result in adimunition of other foam properties or an increase in the density of thefoam, or as mentioned above, introduce undesirable VOCs into thefinished products. In certain embodiments, the inventive foams arecharacterized in that, in addition to the combinations of physicalproperties described above, they contain little or no graft polyol.

In certain embodiments, the inventive foam compositions described aboveare further characterized in that they contain less than 20% graft-typepolyol additives. In certain embodiments, the inventive foamcompositions described above are further characterized in that theycontain less than 10% graft-type polyol additives. In certainembodiments, the inventive foam compositions described above are furthercharacterized in that they contain less than 5% graft-type polyoladditives. In certain embodiments, the inventive seating foamcompositions described above are further characterized in that theycontain less than 3% graft-type polyol additives. In certainembodiments, the inventive seating foam compositions described above arefurther characterized in that they contain less than 2% graft-typepolyol additives. In certain embodiments, the inventive seating foamcompositions described above are further characterized in that theycontain less than 1% graft-type polyol additives. In certainembodiments, the inventive seating foam composition described above arefurther characterized in that they do not contain graft-type polyoladditives.

In certain embodiments, such filled polyols are selected from: polyureadispersion polyols (i.e. Poly Harnststoff Dispersion (PHD) polyols);Polyurethane dispersion polyols (i.e. Polyisocyanate poly additionpolyols (PIPA); Epoxy dispersion polyols; Aminoplast dispersions,acrylic polyols and the like. They are used to increase the load-bearingproperties of low-density high-resiliency (HR) foam, as well as addtoughness to microcellular foams and cast elastomers. However, thesematerials increase the cost of the foams and sometimes result in adimunition of other foam properties such as resilience or an increase inthe density of the foam. In certain embodiments, the inventive foams arecharacterized in that in addition to the combinations of physicalproperties described above, they contain little or no filled polyol.

In certain embodiments, the inventive foam compositions described aboveare further characterized in that they contain less than 5% filledpolyol additives. In certain embodiments, the inventive seating foamcompositions described above are further characterized in that theycontain less than 3% filled polyol additives. In certain embodiments,the inventive seating foam compositions described above are furthercharacterized in that they contain less than 2% filled polyol additives.In certain embodiments, the inventive seating foam compositionsdescribed above are further characterized in that they contain less than1% filled polyol additives. In certain embodiments, the inventiveseating foam compositions described above are further characterized inthat they do not contain graft-type, filled, or acrylic polyoladditives.

While not necessarily explicitly described, further variations of thefoam compositions described above comprising the additional componentstypical in the formulation of a finished foam are encompassed by thepresent invention. These compositions will be readily apparent to theskilled artisan based on the teachings and disclosure herein incombination with common knowledge in the field of polyurethane foamformulation. Therefore, though the present specification may notdescribe them in detail, compositions comprising additional reactioncomponents or additives in the A- and/or B-side formulations (e.g.catalysts, blowing agents, pigments, stabilizers, flame retardants, cellopeners, surfactants, reactive diluents, antimicrobials, solvents, andthe like); are contemplated and encompassed by the present invention.Non-limiting examples of additives that can be utilized in the A-sideand/or B-side mixtures of the inventive foams are described in AppendixC, entitled “Additives” appearing at the end of this specification.

III. ISOCYANATE-TERMINATED PREPOLYMERS WITH UTILITY AS FOAM ADDITIVES

In another aspect, the present invention encompassesisocyanate-terminated polyols derived by reaction of an excess of apolyisocyanate with any of the aliphatic polycarbonate polyols describedabove. Such compositions can be incorporated into the A-side formulationof a polyurethane foam formulation to provide enhanced strength. Scheme1 shows a representative example how such materials can be made:

-   -   where the polycarbonate polyol represents any of those described        above, in Appendix A, or in the classes and subclasses herein,        the diisocyanate represents any reagent capable or reacting with        two alcohols to form two urethane linkages, and where g is 0, or        an integer up to about 10.

Preferably, g is small so that the Mn of the prepolymer remainsrelatively low and the material can be dissolved in a typicalpolyurethane A-side mixture without making it overly viscous. In certainembodiments, the average value of g in the propolymer composition isless than 10, less than 5, less than 4, less than 3, less than 2, orless than 1.

Prepolymers of the present invention may also derive from higherfunctional polyols and/or higher functional isocyanates including thosedescribed in appendices A and B appended hereto.

In another aspect, the present invention encompasses comprising thereaction product between an isocyanate component and a polyol componentwherein the isocyanate component comprises from about 1% to about 20%weight percent of an isocyanate-terminated prepolymer comprising apolyol derived from the copolymerization of CO₂ with one or moreepoxides.

EXAMPLES

The present invention is illustrated by the following examples. It is tobe understood that the particular examples, materials, amounts, andprocedures are to be interpreted broadly in accordance with the scopeand spirit of the invention as set forth herein.

Example 1: High Strength Flexible Foams

Presented below are the formulations of high strength flexiblepolyurethane foams according to the principles of the present invention.These materials were made using aliphatic polycarbonate polyol additivesas defined herein. Specifically, the aliphatic polycarbonate polyolshereinafter also referred to as “Novomer Polyols” used in theformulations below have the following properties:

Property 58-103-C 74-276 Acid Value, mg KOH/g 0.28 0.51 Hydroxyl Value,mg KOH/g 119 61.1 Mn (GPC) 1,270 2,213 Mw (GPC) 1,370 2,443Polydispersity, Mw/Mn 1.07 1.06 Glass Transition Temp. (DSC), Tg −5° C.−5.5° C. Viscosity, cPs 4,990 @ 80° C. —

Polyol 58-103-C is a linear 1270 g/mol poly(propylene carbonate) polyolinitiated with dipolypropylene glycol (a mixture of isomers) having aPDI of 1.06, greater than 99% —OH end groups and greater than 99%carbonate linkages (exclusive of the ether bonds in the dipropyleneglycol). This polyol conforms to the formula:

where n is, on average in the composition, approximately 5.6.

Polyol 74-276 is a linear 2200 g/mol poly(propylene carbonate) polyolinitiated with 425 g/mol polypropylene glycol (mixture of isomers)having a PDI of 1.06, greater than 99% —OH end groups and greater than99% carbonate linkages (exclusive of the ether bonds in thepolypropylene glycol). This polyol conforms to the formula:

where k is on average about 6.8, and n is on average in the compositionapproximately 8.7.

The objective of this study was to determine the effect of CO₂-basedpoly(propylene-carbonate) diols (PPC diols) as additives in a model highresilient (HR) flexible polyurethane foam.

The effect of these PPC diols on load bearing and other properties offree-rise and molded flexible foams were evaluated in comparison to HRflexible foams formulated with and without a commercial graft polyol.

EXPERIMENTAL

Raw Materials

A list of raw materials used in this evaluation is shown in Table 1. Allmaterials were used as received from suppliers including Novomerpolyols.

In foaming experiments, a formulation targeting high resilient flexiblefoams was used as reference. This formulation is based on Poly-G 85-29ethylene oxide tipped polyether triol (polyol). Lumulse POE 26(ethoxylated glycerol) was used as reactive cell opener. Diethanol aminewas used as a co-catalyst and cross-linker.

Preparation and Testing of Foams

Free rise water-blown foams were prepared with 5%, 10%, 15%, 20%, and25% Novomer 58-103C and Novomer 74-276 polyols, respectively, which werecompatible with Poly-G 85-29 polyol (Tables 2-4). All foams wereprepared at 90 Isocyanate Index with Mondur MRS-2, which is a 2,4′-MDIrich isocyanate (Tables 3-5).

Molded foams were prepared with 10% and 20% Novomer 58-103C. Referencemolded foams were also prepared with and without graft polyol SpeciflexNC-701.

Free-rise foams were prepared using a standard laboratory hand-mixingprocedure. Foaming profiles, including cream time, gel time, and risetime were measured on all foams. After the rise time, the foams wereimmediately placed in an air-circulating oven preheated at 80° C. for 30minutes to complete the cure.

Molded foams were prepared using an aluminum mold with 12×12×2 inchdimensions preheated at 69° C. Demolding time was 4.5 minutes.

All foams were aged under room conditions for minimum one week beforetesting. The following properties were measured according to ASTM D3574-08:

-   -   Foam Density (Test A)    -   Resilience via Ball Rebound (Test H)    -   Tensile Strength at Break (Test E)    -   Elongation at Break (Test E)    -   Tear Strength (Test F)    -   CFD, Compression Force Deflection (Test C)    -   Hysteresis (Procedure B—CFD Hysteresis Loss)    -   Dry Constant Deflection Compression Set (Test D)    -   Wet Constant Deflection Compression Set (Test D & Wet Heat        Aging, Test L)    -   Tensile strength and Elongation after Dry Heat Aging for 22        hours at 140° C. (Modified Heat Aging Test K)

TABLE 1 Materials Designation Type Supplier POLYOLS Poly-G 85-29Ethylene oxide caped polyether Arch polyol (triol) Chemicals HydroxylValue = 27.4 mg KOH/g; Eq. wt. = 2047.445 Viscosity @ 25° C. = 1150 cPsSpeciflex NC-701 Grafted polyether polyol containing DOW copolymerizedstyrene and acrylonitrile Hydroxyl Value = 23.0 mg KOH/g; Eq. wt. =2439.13 Viscosity @ 25° C. = 5070 mPa · s Novomer 58-103-C NovomerPoly(Propylene Carbonate) NOVOMER Hydroxyl Value = 119 mg KOH/g; Eq. wt.= 471.43 Acidity Value = 0.28 mg KOH/g Viscosity @ 25° C. = 1.25 × 10⁶cPs Viscosity @ 80° C. = 4990 cPs Novomer 74-245 Novomer Poly(PropyleneCarbonate) NOVOMER Hydroxyl Value = 34.8 mg KOH/g; Eq. wt. = 1612.07Viscosity @ 80° C. = 49,650 cPs Novomer 74-266 Novomer Poly(PropyleneCarbonate) NOVOMER Hydroxyl Value = 63 mg KOH/g; Eq. wt. = 890.47Acidity Value = 0.24 mg KOH/g Viscosity @ 80° C. = 27,240 cPs Novomer74-276 Novomer Poly(Propylene Carbonate) NOVOMER polyol initiated withPPG 600 MW Hydroxyl Value = 61.1 mg KOH/g; Acidity Value = 0.51 mg KOH/gEq. wt. = 918.47 SURFACTANTS Tegostab B 4690 Polyether/Silicone Oil MixEvonik Eq. Wt. = 1335.7 CELL OPENER Lumulse POE 26 Hydroxyl Value =134.8 mg KOH/g Lambent Eq. Wt. = 416.2 CHAIN EXTENDERS DiethanolamineDiethanolamine (Eq. Wt. = 35.04) Aldrich CATALYSTS Dabco 33LV 33%Triethylene diamine in Air Products dipropylene glycol Niax A1bis(2-dimethylaminoethyl) ether Momentive ISOCYANATES Mondur MRS-2 2,4′rich diphenylmethane Bayer diisocyanate (F = 2.2; Eq. wt. = 130.03; %NCO = 32.30%)

Results

Polyol Reactivity

Polyurethane foams were prepared at 5%, 10%, 15%, 20% and 25% asreplacement for conventional polyol Poly-G 85-29 in model HR flexiblefoam formulation. Introduction of PPC polyol 58-103-C polyol intoreference foam formulation as drop-in replacement for Poly-G 85-29 didnot significantly affect the reaction profile (foaming profile) measuredas cream time, gel time, and rise time. However, foams exhibited closedcell structure and shrank after preparation (Table 3A). Stable foamswith open cell structure were obtained after adjustment in catalysis andafter increasing the amount of diethanolamine (reactivecatalyst/cross-linker) from 1 to 2 parts by weight (Tables 3A and 3B).

Foams based on PPC polyol 74-276 polyol were prepared using the samecatalytic package as that used for foams based on Novomer 58-103Cpolyol. No significant difference in reactivity between these twopolyols was observed (Tables 3 and 4).

Apparent Foam Cell Structure and Density

Free-rise foams based on Novomer polyols exhibited similar white colorto the reference foams prepared with Poly-G 85-29 polyol as sole polyoland reference foams prepared with 10% and 25% graft polyol SpeciflexNC-701. The apparent cell structure of foams with Novomer polyols wasuniform and similar to the reference foams.

Density of the free-rise foams did not change significantly withreplacement of the reference polyol with 5%-25% Novomer polyols (Tables3 and 4).

TABLE 3A Formulation screening of PU foams based on 58-103-C PolyolDesignation 1 2 3 4 5 Sample designation Eqv. 10%-58- 10%-58- 10%-58-10%-58- F Weight REF-1 103-C-1 103-C-2 103-C-3 103-C-4 Polyol systemPoly-G 85-29 3 2047.5 97 87.3 87.3 87.3 87.3 Novomer 58-103-C 471.43 09.7 9.7 9.7 9.7 Water 2 9 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26 416.2 3 3 33 3 Tegostab B 4690 1335.7 1 1 1 1 1 Dabco 33LV 105 0.8 0.8 0.8 0.8 0.8Diethanolamine 35.04 1 1 0.6 0.4 0.4 Niax A-1 233.7 0.1 0.1 0.1 0.1 0.15Isocyanate System Mondur MRS-2 130.03 57.12 59.42 58.09 57.42 57.44Isocyanate Index 90 90 90 90 90 % Novomer polyol 0% 10% 10% 10% 10% ontotal polyols Reaction Profile of Free-rise Mix time, sec. 7 7 7 7 7Cream time, sec.  10 ± 0.6 9 12 13 10 Gel time, sec.  49 ± 1.0 39 51 5148 Rise time, sec.  83 ± 1.5 68 99 106 107 Post-curing time 30 min 30min 30 min 30 min 30 min & temperature* @ 80° C. @ 80° C. @ 80° C. @ 80°C. @ 80° C. Properties Free-rise density, pcf 2.26 — — — — Resilience, %60.55 ± 0.73  — — — — Tensile Strength, psi 14.31 ± 1.06  — — — —Elongation at Break, % 104.53 ± 7.92  — — — — Tear Strength, lbf/in 2.70± 0.05 — — — — CFD @ 25%, psi 0.20 ± 0.02 — — — — CFD @ 50%, psi 0.34 ±0.03 — — — — CFD @ 65%, psi 0.59 ± 0.05 — — — — Hysteresis 31.08 ± 1.16 — — — — Tensile Strength 13.26 ± 0.58  — — — — (Dry Heat Aged), psiElongation at Break 128.05 ± 10.50  — — — — (Dry Heat Aged), % DryCompression Set, %  5.3 ± 0.68 — — — — Wet Compression Set, %  7.9 ±0.73 — — — — SAG factor (65/25)** 2.95 — — — — SAG factor (50/25)** 1.7— — — — Comments No shrinkage, Shrinkage, Shrinkage, Shrinkage,Shrinkage, open cells; closed cells; closed cells; closed cells; closedcells; *Samples were placed in an oven, for post-curing, after risetime. Samples were cut & crushed after the first 10 minutes of curing.**SAG factor: CFD@65%/CFD25% and CFD@50%/CFD25%

TABLE 3B Formulation screening of PU foams based on Novomer 58-103-CPolyol Designation 1 2 3 4 5 6 Sample designation Eqv. 5%-58- 10%-58-15%-58- 20%-58- 25%-58- 25%-58- F Weight 103-C-1 103-C-5 103-C-1 103-C-1103-C-1 103-C-2 Polyol system Poly-G 85-29 3 2047.5 92.15 87.3 82.4577.6 72.75 72.25 Novomer 58-103-C 471.43 4.85 9.7 14.55 19.4 24.25 24.25Water 2 9 3.6 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26 416.2 3 3 3 3 3 3Tegostab B 4690 1335.7 1 1 1 1 1 1 Dabco 33LV 105 0.5 0.5 0.5 0.5 0.80.5 Diethanolamine 35.04 2 2 2 2 0.6 2 Niax A-1 233.7 0.1 0.1 0.1 0.10.1 0.10 Isocyanate System Mondur MRS-2 130.03 61.50 62.43 63.35 64.2860.87 65.21 Isocyanate Index 90 90 90 90 90 90 % Novomer polyol 5% 10%15% 20% 25% 25% on total polyols Reaction Profile of Free-rise Mix time,sec. 7 7 7 7 7 7 Cream time, sec. 11  13 ± 0.6  12 ± 0.6  12 ± 0.6 9  11± 0.6 Gel time, sec. 44  52 ± 1.2  52 ± 1.7  50 ± 0.6 45  49 ± 2.6 Risetime, sec. 87  87 ± 2.5 103 ± 8.7   98 ± 1.5 100  84 ± 1.7 Post-curingtime 30 min 30 min 30 min 30 min 30 min 30 min & temperature* @ 80° C. @80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. Properties Free-rise density,pcf 2.41 2.16 2.19 2.07 — 2.13 Resilience, % 55.05 ± 1.47  42.80 ± 1.90 38.96 ± 1.50  36.0 ± 0.70 — 31.8 ± 1.30 Tensile Strength, psi 13.24 ±0.77  15.68 ± 1.89  18.14 ± 1.85  18.93 ± 1.94  — 18.99 ± 2.5 Elongation at Break, % 105.23 ± 7.70  113.32 ± 14.06  105.75 ± 7.91 130.54 ± 13.35  — 99.68 ± 13.02 Tear Strength, lbf/in 3.29 ± 0.18 3.73 ±0.29 3.82 ± 0.25 4.45 ± 0.36 — 4.80 ± 0.20 CFD @ 25%, psi 0.27 ± 0.050.32 ± 0.04 0.38 ± 0.03 0.45 ± 0.04 — 0.70 ± 0.05 CFD @ 50%, psi 0.44 ±0.08 0.53 ± 0.11 0.65 ± 0.07 0.74 ± 0.07 — 1.13 ± 0.09 CFD @ 65%, psi0.78 ± 0.15 0.94 ± 0.21 1.15 ± 0.17 1.28 ± 0.15 — 1.99 ± 0.20 Hysteresis39.21 ± 0.15  44.83 ± 2.94  51.41 ± 0.08  62.09 ± 2.31  — 68.55 ± 3.08 Tensile Strength — 15.03 ± 1.66  — — — — (Dry Heat Aged), psi Elongationat Break — 112.25 ± 12.55  — — — — (Dry Heat Aged), % Dry CompressionSet, % — 14.0 ± 3.14 — — — — Wet Compression Set, % — 18.4 ± 0.93 — — —— SAG factor (65/25) 2.89 2.94 3.03 2.84 — 2.84 SAG factor (50/25) 1.631.66 1.71 1.64 — 1.61 Comments No shrinkage, No shrinkage, No shrinkage,No shrinkage, Shrinkage, No shrinkage, open cells; open cells; opencells; open cells; closed cells; open cells; *Samples were placed in anoven, for post-curing, after rise time. Samples were cut & crushed afterthe first 10 minutes of curing. ** SAG factor: CFD@65%/CFD25% andCFD@50%/CFD25%

TABLE 4 Formulation screening of PU foams based on 74-276 PolyolDesignation 1 2 3 4 5 Sample designation Eqv. 5%-74- 10%-74- 15%-74-20%-74- 25%-74- F Weight 276-1 276-1 276-1 276-1 276-1 Polyol systemPoly-G 85-29 3 2047.5 92.15 87.3 82.45 77.6 72.75 Novomer 74-276 918.464.85 9.7 14.55 19.4 24.25 Water 2 9 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26416.2 3 3 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 1 Dabco 33LV 105 0.5 0.50.5 0.5 0.5 Diethanolamine 35.04 2 2 2 2 2 Niax A-1 233.7 0.1 0.1 0.10.1 0.1 Isocyanate System Mondur MRS-2 130.03 60.91 61.26 61.60 61.9462.28 Isocyanate Index 90 90 90 90 90 % Novomer polyol 5% 10% 15% 20%25% on total polyols Reaction Profile of Free-rise Mix time, sec. 7 7 77 7 Cream time, sec. 11 10 ± 1  10 11 11 Gel time, sec. 49  47 ± 1.0 4445 46 Rise time, sec. 88  87 ± 1.3 83 90 92 Post-curing time 30 min 30min 30 min 30 min 30 min & temperature* @ 80° C. @ 80° C. @ 80° C. @ 80°C. @ 80° C. Properties Free-rise density, pcf 2.27 2.38 2.24 2.28 2.35Resilience, % 55.10 ± 1.40  49.12 ± 1.47  44.46 ± 1.27  38.53 ± 0.73 36.42 ± 1.47  Tensile Strength, psi 13.24 ± 0.77  15.34 ± 1.26  — — —Elongation at Break, % 105.23 ± 7.70  100.19 ± 6.15  — — — TearStrength, lbf/in 3.29 ± 0.18 3.21 ± 0.17 — — — CFD @ 25%, psi 0.28 ±0.03 0.36 ± 0.05 0.35 ± 0.05 0.45 ± 0.07 0.53 ± 0.08 CFD @ 50%, psi 0.47± 0.05 0.59 ± 0.09 0.56 ± 0.07 0.75 ± 0.11 0.87 ± 0.13 CFD @ 65%, psi0.86 ± 0.11 1.05 ± 0.18 0.96 ± 0.11 1.35 ± 0.18 1.57 ± 0.23 Hysteresis35.10 ± 2.5  41.96 ± 1.87  46.15 ± 2.89  54.59 ± 1.06  56.45 ± 1.72 Tensile Strength 12.27 ± 1.02  13.95 ± 0.81  — — — (Dry Heat Aged), psiElongation at Break 93.45 ± 7.49  105.67 ± 5.20  — — — (Dry Heat Aged),% Dry Compression Set, %  6.7 ± 1.71  8.2 ± 2.61 — — — Wet CompressionSet, % 12.7 ± 0.83 14.7 ± 2.94 — — — SAG factor (65/25) 3.07 2.92 2.743.00 2.96 SAG factor (50/25) 1.68 1.64 1.60 1.67 1.64 Comments Noshrinkage, No shrinkage, No shrinkage, No shrinkage, No shrinkage, opencells; open cells; open cells; open cells; open cells; *Samples wereplaced in an oven, for post-curing, after rise time. Samples were cut &crushed after the first 10 minutes of curing. ** SAG factor:CFD@65%/CFD25% and CFD@50%/CFD25%

TABLE 5 Formulation screening of PU foams based on Speciflex NC-701Polyol Designation 1 2 3 4 5 Sample designation Eqv. 10%-NC- 25%-NC- FWeight 701-1 701-1 Polyol system Poly-G 85-29 3 2047.5 87.3 72.75Speciflex NC-701 2244 9.7 24.25 Water 2 9 3.6 3.6 Lumulse POE 26 416.2 33 Tegostab B 4690 1335.7 1 1 Dabco 33LV 105 0.8 0.8 Diethanolamine 35.041 1 Niax A-1 233.7 0.1 0.1 Isocyanate System Mondur MRS-2 130.03 57.0156.18 Isocyanate Index 90 90 % Novomer polyol 10% 25% on total polyolsReaction Profile of Free-rise Mix time, sec. 7 7 Cream time, sec. 11 10Gel time, sec. 42 33 Rise time, sec. 64 47 Post-curing time 30 min 30min & temperature* @ 80° C. @ 80° C. Properties Free-rise density, pcf2.26 2.29 Resilience, % 54.20 ± 1.47 51.24 ± 1.94  Tensile Strength, psi13.65 ± 2.07 14.79 ± 0.98  Elongation at Break, % 109.16 ± 9.65  91.96 ±11.29 Tear Strength, lbf/in  3.10 ± 0.20 3.08 ± 0.75 CFD @ 25%, psi 0.30 ± 0.03 0.41 ± 0.05 CFD @ 50%, psi  0.51 ± 0.05 0.69 ± 0.06 CFD @65% psi  0.91 ± 0.11 1.22 ± 0.11 Hysteresis 33.86 ± 3.17 37.78 ± 3.16 Tensile Strength 12.65 ± 0.88 — (Dry Heat Aged), psi Elongation at Break125.92 ± 7.77  — (Dry Heat Aged), % Dry Compression Set, %  7.3 ± 1.31 —Wet Compression Set, %  8.7 ± 1.64 — SAG factor (65/25) 3.03 2.97 SAGfactor (50/25) 1.70 1.68 Comments No shrinkage, No shrinkage, opencells; open cells; *Samples were placed in an oven, for post-curing,after rise time. Samples were cut & crushed after the first 10 minutesof curing. ** SAG factor: CFD@65%/CFD25% and CFD@50%/CFD25%

TABLE 6 Molded foams Designation 1 2 3 4 Sample designation Eqv. 10%-58-20%-58- F Weight REF-1 NC-701 103-C-5 103-C-1 Polyol system* Poly-G85-29 3 2047.5 97 87.3 87.3 77.6 Novomer 58-103-C 471.43 0 — 9.7 19.4Speciflex NC-701 2244 9.7 Water 2 9 3.6 3.6 3.6 3.6 Lumulse POE 26 416.23 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 Dabco 33LV 105 0.8 0.8 0.5 0.5Diethanolamine 35.04 1 1 2 2 Niax A-1 233.7 0.1 0.1 0.1 0.1 IsocyanateSystem Mondur MRS-2 130.03 57.12 57.01 62.43 64.28 Isocyanate Index 9090 90 90 % Novomer polyol 0% 0% 10% 20% on total polyols ReactionProfile 7 Mix time, sec. 7 7 7 7 De-molding time 4:30 min 4:30 min 4:30min 4:30 min & temperature** @ 70° C. @ 70° C. @ 70° C. @ 70° C.Properties Molded foam density, pcf 3.30 3.31 3.43 3.14 Resilience, %55.05 ± 1.4  52.93 ± 0.73  38.95 ± 1.5  36.0 ± 0.73 CFD @ 25%, psi 0.55± 0.03 0.57 ± 0.06 0.86 ± 0.03 1.01 ± 0.06 CFD @ 50%, psi 0.88 ± 0.040.87 ± 0.10 1.40 ± 0.04 1.59 ± 0.15 CFD @ 65%, psi 1.58 ± 0.22 1.43 ±0.20 2.45 ± 0.05 2.74 ± 0.32 SAG factor (65/25) 2.87 2.51 2.85 2.71 SAGfactor (50/25) 1.60 1.53 1.63 1.57 *The amount used for preparation ofmolded foams was twice the amount shown in the table **Mold was heatedat 70° C.; De-molding time was 270 sec.

The apparent cell structure of molded foams prepared with 10% and 20%58-103C PPC polyol was uniform and similar to the reference foamsprepared with Poly-G 85-29 polyol as sole polyol and reference foamsprepared with 10% graft polyol Speciflex NC-701.

Foam Physical Properties

Reference free-rise foams prepared with a graft polyol (SpeciflexNC-701) also exhibited somewhat lower resilience and somewhat higherhysteresis in comparison to the reference foam prepared with base polyol(Poly-G 85-29) as sole polyol (Tables 3A and 5). In comparison to thefoams based on graft polyols, foams based on Novomer poloyols exhibitedsomewhat lower resilience and somewhat higher hysteresis at the sameload (Tables 3B, 4, and 5).

All foams prepared with Novomer polyols, included molded foams,exhibited relatively high resilience and can be classified as HighResilient (HR) PU foams.

In general, the tensile strength increased with introduction of Novomerpolyols. With introduction of Novomer polyol the elongation did notchange significantly (Tables 3 and 4). Tensile strength and elongationof foams based on Novomer polyols was similar to those based on graftpolyol at the same load (Tables 3-5). These results indicate that thefoam strength (toughness) increases by introduction of the Novomerpolyols.

The tear strength measured on foams prepared with Novomer polyols wassignificantly higher in comparison to the reference foam prepared withbase polyol as sole polyol (Tables 3 and 4). The tear strength of foamsbased on Novomer polyols were somewhat higher in comparison to thereference foams prepared with graft polyol (Tables 3-5). These resultsalso indicate that the foam strength (toughness) increases byintroduction of the Novomer polyols.

Free-rise foams based on Novomer polyols exhibited significantly higherCompression Force Deflection (CFD) at 25%, 50%, and 65% deflections incomparison to the reference foam prepared with base polyol as solepolyol (Tables 3 and 4; FIGS. 1-2) and slightly higher in comparison tothe reference foams based on graft polyol (Tables 3-5; FIG. 3). Theseresults clearly indicate that Novomer polyols improve the load bearingproperties of the flexible foams. More importantly, the SAG factor wasnot affected by the introduction of Novomer polyols into foamformulations (Tables 3-5; FIGS. 4 and 5). Similar effect of Novomerpolyol on CFD properties was observed in the case of molded foams (Table6).

Slight decrease in tensile strength was observed in all foams that weretested for resistance to dry aging for 22 hours at 140° C. However, nomajor difference in retention of properties was observed betweenreference foams with and without graft polyol and foams prepared withNovomer polyols (Tables 3-5).

Conclusions

Reactivity of Novomer polyols was comparable to the reactivity of thereference polyol Poly-G 85-29 and graft polyol Speciflex NC-701.However, in order to get open cell structure some adjustments incatalysis and amount of diethanolamine (reactive catalyst/cross-linker)was required.

Freer-rise foams prepared with 5%-25% Novomer polyols exhibited uniformcell structure. Both the density and apparent cell structure of thesefoams were comparable to the reference foams prepared with and withoutgraft polyol.

All foams prepared with 5%-25% Novomer polyols exhibited relatively highresilience and can be classified as High Resilient (HR) PU foams. Allthese foams exhibited comparable properties to the reference foams whichmeets most of the properties specified by Chrysler Material Standard:MS-DC-649 for “Cellular, Molded Polyurethane High Resilient (HR) TypeSeat Applications”.

The tensile strength and tear strength properties of foams prepared withNovomer polyols were better in comparison to the reference foams. Theretention of stress-strain properties with heat aging was not affectedby introduction of Novomer polyols.

Results of CFD measurements clearly indicate an increase in load bearingproperties of free-rise and molded foams based on Novomer polyolswithout affecting the SAG (comfort) factor.

Example 2: Viscoelastic Foam Compositions

Presented below are the formulations of viscoelastic polyurethane foamsaccording to the principles of the present invention. These materialswere made using aliphatic polycarbonate polyol additives as definedherein. Specifically, the aliphatic polycarbonate polyols hereinafteralso referred to as “Novomer Polyols” used in the formulations belowhave the following properties:

58-103-C 74-217 74-277 Acid Value, mg KOH/g 0.28 0.02 0.01 HydroxylValue, mg KOH/g 119 169.95 67.07 Mn (GPC) 1,270 810 2290 Mw (GPC) 1,370920 2400 Polydispersity, Mw/Mn 1.07 1.13 1.05 Glass Transition Temp. −5°C. −20° C. −5° C. (DSC), Tg Viscosity, cPs 4,990 330 3700 @ 80° C. @ 75°C.− @ 75 ° C.

Polyol 58-103-C is a linear 1270 g/mol poly(propylene carbonate) polyolinitiated with dipolypropylene glycol (a mixture of isomers) having aPDI of 1.06, greater than 99% —OH end groups and greater than 99%carbonate linkages (exclusive of the ether bond in the dipropyleneglycol). This polyol conforms to the formula:

where n is, on average in the composition, approximately 5.6.

Polyol 74-217 is a linear 810 g/mol poly(propylene carbonate) polyolinitiated with dipolypropylene glycol (a mixture of isomers) having aPDI of 1.13, greater than 99% —OH end groups and greater than 99%carbonate linkages (exclusive of the ether bond in the dipropyleneglycol). This polyol conforms to the formula:

where n is, on average in the composition, approximately 3.3.

Polyol 74-277 is a linear 2400 g/mol poly(propylene carbonate) polyolinitiated with 600 g/mol polypropylene glycol (mixture of isomers)having a PDI of 1.05, greater than 99% —OH end groups and greater than99% carbonate linkages (exclusive of the ether bonds in thepolypropylene glycol). This polyol conforms to the formula:

where k is on average about 10, and n is on average in the compositionapproximately 9.

The effect of PPC diols on load bearing (CFD) and other properties ofvisco-elastic polyurethane foams were evaluated in this study. Foamswere also prepared using a mixture of Novomer PPC polyols. Mondur MRS-2with high content of 2,4′-MDI was used as an isocyanate in preparationof foams. Properties of visco-elastic foams prepared with NOVOMERpolyols were compared to properties of reference model formulationprepared with conventional polyols.

Raw Materials

A list of raw materials used in this evaluation is shown in Table 1B.All materials were used as received including Novomer polyols.

TABLE 1B Materials Designation Type Supplier POLYOLS Novomer PolyolNovomer Poly(Propylene Carbonate) Novomer Batch # 58-103-C HydroxylValue = 119 mg KOH/g; Eq. wt. = 471.43 Acidity Value = 0.28 mg KOH/gNovomer Polyol Hydroxyl Value = 169.95 mg KOH/g; Novomer Batch # 74-217Eq. wt. = 330.1 Acidity Value = 0.02 mg KOH/g Novomer Polyol HydroxylValue = 67.07 mg KOH/g; Novomer Batch # 74-277 Eq. wt. = 836.4 AcidityValue = 0.01 mg KOH/g Poly G 30-240 Oxypropylated polyether triol ArchHydroxyl Value = 238 mg KOH/g; Eq. wt. = 235.7 Poly G-76-120 Ethyleneoxide capped polyether triol Arch Hydroxyl Value = 119.3 mg KOH/g; Eq.wt. = 467.5 Poly G-85-34 Ethylene oxide capped polyether triol ArchHydroxyl Value = 35 mg KOH/g; Eq. wt. = 1602.9 SURFACTANTS Tegostab B4690 Polyether/Silicone Oil Mix Evonik Eq. Wt. = 1335.7 CELL OPENERLumulse POE 26 Hydroxyl Value = 134.8 mg KOH/g Lambent Eq. Wt = 416.2CHAIN EXTENDER DEG Diethylene glycol Interstate Chem. Com. CATALYSTSDabco 33LV 33% Triethylene diamine in Air Products dipropylene glycolNiax A1 bis(2-dimethylaminoethyl) ether Momentive ISOCYANATES MondurMRS-2 2,4′ rich diphenylmethane Bayer diisocyanate (F = 2.2; Eq. wt. =129.9; % NCO = 32.35) FILLER Calcium carbonate Calcium carbonate,Spectrum Powder - TechnicalPreparation and Testing of Foams

Free rise water-blown foams were prepared with 0%, 10%, and 20% Novomer58-103-C, Novomer 74-217, and Novomer 74-277 polyols as replacements forpetroleum based commercial polyols. VE foams were also prepared using amixture of the three Novomer polyols up to 30% and 45% levels asreplacements for the petroleum based commercial polyols (Tables 2B-5B).Reference VE foams and VE foams based on Novomer polyols were alsoprepared with CaCO₃ as filler (Tables 2B-5B).

Most of the VE foams in this Example were prepared at an IsocyanateIndex of 70 with Mondur™ MRS-2, which is a 2,4′-MDI rich isocyanate(Tables 2B-5B). Foams based on 30% and 45% mixture of the three Novomerpolyols were also prepared at an Isocyanate Index of 80 (Table 5B).

Free-rise foams were prepared using a standard laboratory hand-mixingprocedure. Foaming profiles, including cream time, gel time, and risetime were measured on all foams. After the rise time, the foams wereimmediately placed in an air-circulating oven preheated at 70° C. for 60minutes to complete the cure.

The full characterization was carried out on selected foams after agingfor a minim 7 days according to ASTM D 3574-08 as follows:

-   -   Foam Density (Test A),    -   Resilience via Ball Rebound (Test H),    -   Tensile Strength at Break (Test E),    -   Elongation at Break (Test E),    -   Tear Strength (Test F),    -   CFD, Compression Force Deflection (Test C),    -   Hysteresis (Procedure B—CFD Hysteresis Loss),    -   Dry Constant Deflection Compression Set (Test D),    -   Wet Constant Deflection Compression Set (Test D & Wet Heat        Aging, Test L)

Recovery Time was measured on Instron Tester using in-house protocol.The following measurement parameters were employed:

-   -   Sample dimensions: 2″×2″×1″    -   Indentor Foot Area: 64 mm²    -   Speed: 500 mm/min    -   Indentation: 80%    -   Hold Time: 60 sec.

The recovery time was measured according to the following protocol:Place the test specimen on the supporting plate. Bring the indentor footinto contact with the specimen. Immediately indent the specimen 80% ofits initial thickness at a speed of 500 mm/min and hold for 60 seconds.After 60 seconds dwell time, return the indentor to 0% deflection at 500mm/min, starting the stopwatch immediately upon initiating the upwardmovement of the indentor. Stop the watch as soon as the imprint of theindentor foot is not visible, and record the time. Repeat the process on2 additional specimens and calculate the average time.

Glass transition temperature was measured via the following methods:

-   -   DSC (DSC Q10 from TA instrument) under nitrogen at heating rate        of 20° C. per minute in a temperature rate between −80° and        +200° C.    -   DMA (DMA 2980 from TA Instrument) under nitrogen at heating rate        of 3° C. per minute in a temperature rate between −80° and +130°        C.        Results

A model VE foam formulation was based on three different commercialpolyether triols: Poly-G 30-240, Poly-G 76-120, and Poly-G 85-34 withequivalent weights of ˜236, ˜468, and ˜1603, respectively (Tables1B-5B). Ethoxylated glycerol Lumulse POE 26 with equivalent weight of˜416 was used as a cell opening polyol (Tables 1B-5B). Diethylene glycol(DEG) was used as a chain extender. Dabco 33LV and Niax A-1 were used ascatalysts. Dabco 33LV catalyst promotes gelling reaction (reaction ofisocyanate with polyol) and blowing reaction (reaction of isocyanatewith water). Niax A-1 is a blowing catalyst.

The reactivity of the PU systems was not affected significantly after10% and 20% drop-in replacement of any of commercial polyols (Tables2B-4B) including the cell opening polyol (Table 2B) with Novomer polyls.The reactivity of the PU system was not significantly affected after 30%and 45% drop-in replacement of commercial polyols with a mixture of thethree Novomer polyols (Table 5B). No adjustment in catalysis wasrequired to obtain open cell foams with Novomer polyols (Tables 2B-5B).

VE foams based on Novomer polyols exhibited a white color similar to thereference foams. The apparent cell structure of foams with Novomerpolyols was uniform and similar to the reference foams.

Foam Physical Properties

Compression Force Deflection (CFD) at 25%, 50%, and 65% deflection wasincreased by introduction of Novomer polyols (Tables 2B-5B and FIGS. 6,10, 12, and 15). CFD values normalized for the density clearly indicatethat foams with Novomer polyol have higher CFD (better load bearingproperties) in comparison to the reference foams (Tables 2B-5B and FIGS.7, 10, 13, and 16). CFD graphs are shown in FIGS. 6-19.

Hysteresis Loss, which is independent of foam density, also increasedwith introduction of Novomer polyols (Tables 2B-5B and FIGS. 8, 11, 14,and 17) which indicates that foams based on Novomer polyols are moreenergy absorbing than the reference foams. In general, Hysteresis Lossis a more reliable measure of energy absorption than resilience measuredvia the Ball Rebound Method. All foams prepared in this study exhibitedvery low resilience of 1% or less (Tables 2B-5B).

The tensile strength (FIGS. 6-20) and tear strength (FIGS. 20-23) of theVE foams was increased by introduction of Novomer polyol 58-103-C as areplacement for Poly-G 76-120 polyols of similar equivalent weight, bothwith and without calcium carbonate filler (compare formulations 1 and 2with formulations 4 and 5 in Table 2B). The tensile and tear strengthsmeasured are consistent with the CFD properties of these foams.

The increase in tensile strength and tear strength properties wasespecially high in foams prepared with a proportional mixture of thethree Novomer polyols at 30% and 45% replacement of the three commercialbase polyols (compare formulations 1 and 2 with formulations 3 and 4 inTable 5B). As expected, with an increase in isocyanate index from 70 to80 the tensile strength and tear strength increased even more in thefoams based on a mixture of Novomer polyols (compare formulations 3 and4 with formulations 5 and 6 in Table 5B).

In most foams tested, the elongation at break was much higher than theelongation (% strain) at maximum load. In order to be consistent, theelongation at maximum load was reported as the elongation. Withoutexception, all foams exhibited elongation greater than 100% (Tables2B-5B).

Recovery time after indentation to 80% of its initial thickness was notsignificantly affected in foams prepared using just one of Novomerpolyols (Tables 2B-4B). However, foams prepared with a proportionalmixture of the three Novomer polyols at 30% and 45% levels asreplacement for base commercial polyols exhibited huge increase in therecovery time in comparison to the reference foam (Table 5). This isconsistent with the hysteresis values of these foams (Table 5B).

Dray and wet compression set was measured on selected number of foams.In all foams containing up to 30% Novomer polyols based on total polyolsboth dry and wet compression sets were relatively low and comparable tothe reference foam (Tables 2B-5B).

DMA and DSC Results

DMA and DSC graphs of selected foams are shown in FIGS. 18-23.Transitions in DMA and DSC graphs are summarized in table on the nextpage.

Reference foam (REF-3, Formulation #1 in Tables 2-5) exhibited Tg at−46° C. which corresponds to first maximum in loss modulus as measuredvia DMA (FIG. 18a ; see Table 1C). Tan delta peak was broad andexhibited low height with maximum at 35° C. In general, the area underTan Delta peak relates to energy absorbing properties; larger areashould relate to higher energy absorbing properties. The foam that haslow Tg and high area under Tan delta curve is considered desirable formemory foams.

Foam based on 20% Novomer 74-217 polyol (Formulation #4 in Table 3B)exhibited a Tg similar to the reference foam, as measured by DMA (SeeTable 1C). The Tg measured via DSC was also similar to the referencefoam (Table 1C). Tan delta max measured on the foam incorporating 20%Novomer 74-217 polyol was at slightly higher temperature in comparisonto the reference foam. However, the tan delta peak was significantlyhigher and area under the peak was significantly larger in comparison tothe reference foam which indicates that the energy absorbing capacity ishigher. These data correlate very well with hysteresis measurements.Hysteresis Loss of Novomer foam was 62% and that of the reference foam36% (Formulations #1 and #4 in Table 3B).

TABLE 1C Transitions Measured via DMA and DSC Foam Formulation # DMAtransitions DSC designation (Table #) Loss Modulus, ° C. Tan delta max.,° C. transitions Reference foam F#1 (T#2B-5B) −46.4 (Tg); 35.25 3.28(Tg) −1.96; +26.1 (broad and low height) PPC-0.8-DPG-20% F#4 (T#3B)−43.9 (Tg); 39.35 6.82 (Tg) 3.08; 29.6(weak) (broad and high) Novomer103C-5 F#3 (T#2B) 3.08 (Tg); 30.2  −2.48 (Tg); 29.3 (broad and mediumhigh) 112 (weak) PPC-2.3-PEOL-20% F#4 (T#4B) −33.49 (Tg); ~40   6.19(Tg); 0.88; 29.28 (broad and high) 114.31 (weak); 159.8 (weak) ISO 80%F#5 (T#5B) −41.38 (Tg); 49.75 13.36 (Tg); 13.81 (broad and high) 108.74(weak) ISO 80%-15 F#6 (T#5B) 28.00 (Tg) 55.74 17.37 (Tg); (broad andhigh) 110.08 (weak)

Foam based on 18% Novomer 58-103-C polyol (Formulation #3 in Table 2B-2)exhibited significantly higher Tg than reference foam, as measured byDMA (FIGS. 18a and 19; see also table above). This shift in Tg measuredvia DMA can be ascribed to the fact that polyether polyol with highequivalent weight of 1603 was replaced with Novomer polyol of relativelylow equivalent weight (471) (Formulations #1 and #3 in Table 2B-2).However, Tg as measured via DSC was detected at slightly lowertemperature in the case of Novomer foam in comparison to the referencefoam (FIGS. 21 and 22; see also table above).

Tan delta max of this Novomer foam was at 30° C., close to the referencefoam. The area under the tan delta peak was higher in comparison to thereference foam which indicates that the energy absorbing capacity ishigher (FIGS. 18 and 19). These results are also consistent withhysteresis measured on these two foams (Formulations #1 and #3 in Table2B).

Foam based on 20% Novomer 74-277 polyol (Formulation #4 in Table 4B)exhibited relatively low Tg (−33.49° C.) as measured via DMA and Tandelta peak is at 40° C., which is broad and high. Both Tg and Tan deltamax are slightly shifted to higher temperatures as compared to referencefoam (FIGS. 18 and 19, Table 1C). Energy absorbing properties asmeasured by DMA correlate very well with hysteresis results. This foamexhibited significantly higher hysteresis in comparison to the referencefoam (Formulation #1 and #4 in Table 4).

Foam prepared by using 30% mixture of 3 different Novomer polyols(Formulation #5 in Table 5B) exhibited low Tg close to the referencefoam as determined via DMA. Tan delta peak was broad and high withmaximum at 50° C., indicating significantly higher energy absorbingcapacity in comparison to the reference foam (FIGS. 18 and 20 a; Table1C). Hysteresis value for this foam was high, (73%) while that of thereference foam was 36% (Formulations #1 and #5 in Table 5B).

Foam prepared by using 45% mixture of 3 different Novomer polyols(Formulation #6 in Table 5B) exhibited relatively high Tg in comparisonto the reference foam and other foams prepared with Novomer polyols(FIGS. 18-20, Table 1C). Tan delta maximum was at 56° C., which issignificantly higher in comparison to other foams. Tan delta peak washigh indicating large energy absorbing capacity, which is consistentwith the hysteresis loss of 83% (Formulation #6 in Table 5B).

Based on DMA measurements it can be concluded that Novomer polyolsimpart energy improved absorbing properties to the foam which is adesirable property viso-elastic foams.

TABLE 2B-1 Visco-elastic foams formulated with Novomer 58-103-C polyolEqv. Designation Weight 1 2 3 4 6 Sample designation REF-3 CaCO3-2Novomer Novomer Novomer 103C 1* 103C-2* 103C-4 Total Novomer 0 0 10 1010 polyols, % Polyol system Novomer 58-103-C 471.4 0 0 10 10 10 Poly G30-240 235.7 21 21 17 21 21 Poly G 76-120 467.5 21 21 17 21 21 Poly G85-34 1602.9 18 18 16 18 8 Lumulse POE 26 416.2 40 40 40 30 40 CaCO3 026 0 0 0 DEG 53.1 2.25 2.25 2.25 2.25 2.25 Water 9 2.3 2.3 2.3 2.3 2.3Tegostab B 4690 1335.7 1.5 1.5 1.5 1.5 1.5 Dabco 33LV 105 0.1 0.1 0.10.1 0.1 Niax A-1 233.7 0.2 0.2 0.2 0.2 0.2 Isocyanate System MondureMRS-2 129.9 49.45 49.45 48.94 49.19 50.81 Isocyanate Index 70 70 70 7070 Reaction Profile of Free-rise Mix time, sec. 10 10 10 10 10 Creamtime, sec. 15.33 14 13 16 14 Gel time, sec. 63.33 52 45 66 56 Rise time,sec. 137.33 136 98 152 83 Post-curing time 60 min 60 min 60 min 60 min60 min & temperature* @70° @70° @70° @70° @70° Properties Free-risedensity, pcf 2.87 ± 0.10 3.37 ± 0.14 2.56 ± 0.17 3.11 ± 0.16 3.15 ± 0.11Resilience, % 0.86 ± 0.23 0.76 ± 0.31 0.25 ± 0.00 0.66 ± 0.14 0.56 ±0.11 CFD @ 25%, psi 0.06 ± 0.01 0.08 ± 0.01 0.06 ± 0.02 0.15 ± 0.03 0.11± 0.01 CFD @ 50%, psi 0.09 ± 0.01 0.12 ± 0.01 0.09 ± 0.02 0.19 ± 0.040.16 ± 0.02 CFD @ 65%, psi 0.14 ± 0.02 0.19 ± 0.02 0.15 ± 0.04 0.28 ±0.07 0.25 ± 0.03 Hysteresis  36 ± 3.22 45.40 ± 1.98  53.86 ± 1.36  68.66± 3.41  39.32 ± 2.51  Tensile Strength, psi 11.33 ± 1.89  9.83 ± 0.5210.89 ± 1.84  17.13 ± 3.97  5.57 ± 1.65 Elongation at Maximum 192 ± 34 163 ± 17  169 ± 66  180 ± 14  108 ± 23  Load, % Tear Strength, lbf/in2.04 ± 0.07 2.45 ± 0.25 2.05 ± 0.24 3.00 ± 0.47 1.94 ± 0.03 RecoveryTime, sec 3.91 ± 1.08 — — — Dry Compression Set  2.7 ± 0.42 — — — — @70° C., % Wet Compression Set  2.2 ± 1.16 — — — — @ 50° C., % Comments*After rise time, samples were placed in an oven for post-curing.

TABLE 2B-2 Visco-elastic foams formulated with Novomer 58-103-C polyolEqv. Designation Weight 1 2 3 4 5 6 Sample designation REF-3 CaCO3-2Novomer FOAM #3 FOAM#4 FOAM #5 58-103C Total Novomer 0 0 18 10 10 20polyols, % Polyol system Novomer 58-103-C 471.4 0 0 18 10 10 20 Poly G30-240 235.7 21 21 21 21 21 21 Poly G 76-120 467.5 21 21 21 11 11 1 PolyG 85-34 1602.9 18 18 0 18 18 18 Lumulse POE 26 416.2 40 40 40 40 40 40CaCO3 0 26 0 0 26 0 DEG 53.1 2.25 2.25 2.25 2.25 2.25 2.25 Water 9 2.32.3 2.3 2.3 2.3 2.3 Tegostab B 4690 1335.7 1.5 1.5 1.5 1.5 1.5 1.5 Dabco33LV 105 0.1 0.1 0.1 0.1 0.1 0.1 Niax A-1 233.7 0.2 0.2 0.2 0.2 0.2 0.2Isocyanate System Mondure MRS-2 129.9 49.45 49.45 51.90 49.43 49.4349.41 Isocyanate Index 70 70 70 70 70 70 Reaction Profile of Free-riseMix time, sec. 10 10 10 10 10 10 Cream time, sec. 15.33 14 14 17 14 14Gel time, sec. 63.33 52 58 63 48 56 Rise time, sec. 137.33 136 83 156129 131 Post-curing time 60 min 60 min 60 min 60 min 60 min 60 min &temperature* @70° @70° @70° @70° @70° @70° Properties Free-rise density,pcf 2.87 ± 0.10 3.37 ± 0.14 3.18 ± 0.17 3.07 ± 0.04 3.53 ± 0.31 3.18 ±0.11 Resilience, % 0.86 ± 0.23 0.76 ± 0.31 0.56 ± 0.11 2.54 ± 0.00 2.54± 0.00 0.51 ± 0.00 CFD @ 25%, psi 0.06 ± 0.01 0.08 ± 0.01 0.08 ± 0.020.08 ± 0.01 0.14 ± 0.03 0.14 ± 0.02 CFD @ 50%, psi 0.09 ± 0.01 0.12 ±0.01 0.12 ± 0.02 0.12 ± 0.01 0.20 ± 0.04 0.19 ± 0.02 CFD @ 65%, psi 0.14± 0.02 0.19 ± 0.02 0.19 ± 0.03 0.19 ± 0.03 0.33 ± 0.07 0.29 ± 0.03Hysteresis  36 ± 3.22 45.40 ± 1.98  42.56 ± 1.14  59.10 ± 0.69  61.70 ±1.08  67.42 ± 1.66  Tensile Strength, psi 11.33 ± 1.89  9.83 ± 0.52 5.20± 0.63 13.83 ± 1.63  16.15 ± 1.62  21.37 ± 0.81  Elongation at Maximum192 ± 34  163 ± 17  124 ± 22  187 ± 5  176 ± 10  213 ± 33  Load, % TearStrength, lbf/in 2.04 ± 0.07 2.45 ± 0.25 1.62 ± 0.25 2.82 ± 0.39 3.14 ±0.32 3.59 ± 0.28 Recovery Time, sec 3.91 ± 1.08 — 3.30 ± 0.95 — — — DryCompression Set  2.7 ± 0.42 —  2.9 ± 2.78 — — — @ 70° C., % WetCompression Set  2.2 ± 1.16 —  0.8 ± 0.38 — — — @ 50° C., % *After risetime, samples were placed in an oven for post-curing.

TABLE 3B Visco-elastic foams formulated with Novomer PPC-0.8-DPG polyolEqv. Designation Weight 1 2 3 4 5 Sample designation REF-3 CaCO3-2 PPC74- PPC 74- FOAM #1 217-10% 217-20% Total Novomer 0 0 10 20 10 polyols,% Polyol system Novomer PPC 74-217 330.1 0 0 10 20 10 Poly G 30-240235.7 21 21 16 11 16 Poly G 76-120 467.5 21 21 16 11 16 Poly G 85-341602.9 18 18 18 18 18 Lumulse POE 26 416.2 40 40 40 40 40 CaCO3 0 26 0 026 DEG 53.1 2.25 2.25 2.25 2.25 2.25 Water 9 2.3 2.3 2.3 2.3 2.3Tegostab B 4690 1335.7 1.5 1.5 1.5 1.5 1.5 Dabco 33LV 105 0.1 0.1 0.10.1 0.1 Niax A-1 233.7 0.2 0.2 0.2 0.2 0.2 Isocyanate System MondureMRS-2 129.9 49.45 49.45 49.30 49.15 49.30 Isocyanate Index 70 70 70 7070 Reaction Profile of Free-rise Mix time, sec. 10 10 10 10 10 Creamtime, sec. 15.33 14 16 16 14 Gel time, sec. 63.33 52 48 48 43 Rise time,sec. 137.33 136 168 147 128 Post curing time 60 min 60 min 60 min 60 min60 min & temperature* @70° @70° @70° @70° @70° Properties Free-risedensity pcf 2.87 ± 0.10 3.37 ± 0.14 3.29 ± 0.11 3.22 ± 0.18 3.76 ± 0.22Resilience, % 0.86 ± 0.23 0.76 ± 0.31 0.50 ± 0.00 0.13 ± 0.03 1.27 ±0.00 CFD @ 25%, psi 0.06 ± 0.01 0.08 ± 0.01 0.10 ± 0.02 0.11 ± 0.03 0.09± 0.01 CFD @ 50%, psi 0.09 ± 0.01 0.12 ± 0.01 0.14 ± 0.03 0.15 ± 0.040.14 ± 0.02 CFD @ 65%, psi 0.14 ± 0.02 0.19 ± 0.02 0.22 ± 0.05 0.24 ±0.08 0.21 ± 0.04 Hysteresis  36 ± 3.22 45.40 ± 1.98  43.62 ± 1.51  61.79± 1.81  57.21 ± 1.96  Tensile Strength, psi 11.33 ± 1.89  9.83 ± 0.5211.55 ± 1.60  10.91 ± 0.37  9.59 ± 0.83 Elongation at Maximum 192 ± 34 163 ± 17  202 ± 16  213 ± 11  153 ± 15  Load, % Tear Strength, lbf/in2.04 ± 0.07 2.45 ± 0.25 1.90 ± 0.15 2.16 ± 0.16 2.39 ± 0.30 RecoveryTime, sec 3.91 ± 1.08 — — 10.48 ± 0.42  — Dry Compression Set  2.7 ±0.42 — —  3.3 ± 1.88 — @ 70° C., % Wet Compression Set  2.2 ± 1.16 — — 1.5 ± 0.99 — @ 50° C., % *After rise time, samples were placed in anoven for post-curing.

TABLE 4B Visco-elastic foams formulated with Novomer 74-277 polyol Eqv.Designation Weight 1 2 3 4 5 Sample designation REF-3 CaCO3-2 74- 74-FOAM #2 277-10% 277-20% Total Novomer 0 0 10 20 10 polyols, % Polyolsystem Novomer 74-277 836.4 0 0 10 20 10 Poly G 30-240 235.7 21 21 21 2121 Poly G 76-120 467.5 21 21 16 11 16 Poly G 85-34 1602.9 18 18 13 8 13Lumulse POE 26 416.2 40 40 40 40 40 CaCO3 0 26 0 0 26 DEG 53.1 2.25 2.252.25 2.25 2.25 Water 9 2.3 2.3 2.3 2.3 2.3 Tegostab B 4690 1335.7 1.51.5 1.5 1.5 1.5 Dabco 33LV 105 0.1 0.1 0.1 0.1 0.1 Niax A-1 233.7 0.20.2 0.2 0.2 0.2 Isocyanate System Mondure MRS-2 129.9 49.45 49.45 49.2849.11 49.28 Isocyanate Index 70 70 70 70 70 Reaction Profile ofFree-rise Mix time, sec. 10 10 10 10 10 Cream time, sec. 15.33 14 14 1113 Gel time, sec. 63.33 52 63 47 46 Rise time, sec. 137.33 136 132 129115 Post-curing time 60 min 60 min 60 min 60 min 60 min & temperature*@70° @70° @70° @70° @70° Properties Free rise density, pcf 2.87 ± 0.103.37 ± 0.14 3.30 ± 0.17 3.09 ± 0.07 3.60 ± 0.16 Resilience, % 0.86 ±0.23 0.76 ± 0.31 0.50 ± 0.00 0.23 ± 0.03 3.05 ± 0.70 CFD @ 25%, psi 0.06± 0.01 0.08 ± 0.01 0.15 ± 0.02 0.15 ± 0.01 0.14 ± 0.02 CFD @ 50%, psi0.09 ± 0.01 0.12 ± 0.01 0.20 ± 0.03 0.20 ± 0.01 0.20 ± 0.03 CFD @ 65%,psi 0.14 ± 0.02 0.19 ± 0.02 0.28 ± 0.05 0.30 ± 0.02 0.31 ± 0.05Hysteresis  36 ± 3.22 45.40 ± 1.98  62.25 ± 3.67  60.96 ± 2.45  55.22 ±1.41  Tensile Strength, psi 11.33 ± 1.89  9.83 ± 0.52 13.05 ± 1.36  7.79± 1.16 16.49 ± 2.24  Elongation at Maximum 192 ± 34  163 ± 17  192 ± 14 196 ± 36  184 ± 4  Load, % Tear Strength, lbf/in 2.04 ± 0.07 2.45 ± 0.252.25 ± 0.16 2.47 ± 0.22 2.85 ± 0.17 Recovery Time, sec 3.91 ± 1.08 — —15.74 ± 0.61  — Dry Compression Set  2.7 ± 0.42 — —  3.8 ± 1.09 — @ 70°C., % Wet Compression Set  2.2 ± 1.16 — — — — @ 50° C., % *After risetime, samples were placed in an oven for post-curing.

TABLE 5B Visco-elastic foams formulated with a mixture of threedifferent Novomer polyols Eqv. Designation Weight 1 2 3 4 5 6 Sampledesignation REF-3 CaCO3-2 ISO ISO- ISO ISO 70%-10 70%-15 80% 80%-15Total Novomer 0 0 30 45 30 45 polyols, % Polyol system Novomer 58-103-C471.4 0 0 10 15 10 15 Novomer 74-217 330.1 0 0 10 15 10 15 Novomer74-277 836.4 0 0 10 15 10 15 Poly G 30-240 235.7 21 21 11 6 11 6 Poly G76-120 467.5 21 21 11 6 11 6 Poly G 85-34 1602.9 18 18 8 3 8 3 LumulsePOE 26 416.2 40 40 40 40 40 40 CaCO3 0 26 0 0 0 0 DEG 53.1 2.25 2.252.25 2.25 2.25 2.25 Water 9 2.3 2.3 2.3 2.3 2.3 2.3 Tegostab B 46901335.7 1.5 1.5 1.5 1.5 1.5 1.5 Dabco 33LV 105 0.1 0.1 0.1 0.1 0.1 0.1Niax A-1 233.7 0.2 0.2 0.2 0.2 0.2 0.2 Isocyanate System Mondure MRS-2129.9 49.45 49.45 48.85 48.55 55.83 55.48 Isocyanate Index 70 70 70 7080 80 Reaction Profile of Free-rise Mix time, sec. 10 10 10 10 10 10Cream time, sec. 15.33 14 14 14 15 15.5 Gel time, sec. 63.33 52 49 45 4847 Rise time, sec. 137.33 136 137 131 137 124 Post-curing time 60 min 60min 60 min 60 min 60 min 60 min & temperature* @70° @70° @70° @70° @70°@70° Properties Free-rise density, pcf 2.87 ± 0.10 3.37 ± 0.14 3.28 ±0.19 3.31 ± 0.14 3.15 ± 0.13 3.02 ± 0.14 Resilience, % 0.86 ± 0.23 0.76± 0.31 0.86 ± 0.14 0.66 ± 0.14 1.47 ± 0.11 — CFD @ 25%, psi 0.06 ± 0.010.08 ± 0.01 0.13 ± 0.02 0.23 ± 0.03 0.36 ± 0.03 0.49 ± 0.07 CFD @ 50%,psi 0.09 ± 0.01 0.12 ± 0.01 0.17 ± 0.02 0.29 ± 0.04 0.49 ± 0.05 0.62 ±0.09 CFD @ 65%, psi 0.14 ± 0.02 0.19 ± 0.02 0.24 ± 0.01 0.41 ± 0.07 0.75± 0.10 0.79 ± 0.13 Hysteresis  36 ± 3.22 45.40 ± 1.98  77.40 ± 3.37 89.87 ± 0.45  72.62 ± 0.97  83.23 ± 1.64  Tensile Strength, psi 11.33 ±1.89  9.83 ± 0.52 14.70 ± 5.31  21.67 ± 13.00 28.77 ± 5.78  29.32 ±3.54  Elongation at Maximum 192 ± 34  163 ± 17  201 ± 20  186 ± 49  192± 15  156 ± 14  Load, % Tear Strength, lbf/in 2.04 ± 0.07 2.45 ± 0.252.49 ± 0.17 3.34 ± 0.22 5.96 ± 0.64 6.44 ± 0.50 Recovery Time, sec 3.91± 1.08 —   89 ± 13.45  524 ± 109.5  39 ± 7.55 177.7 ± 9.29  DryCompression Set  2.7 ± 0.42 —  6.0 ± 3.70 25.2 ± 9.13  2.4 ± 1.82 — @70° C., % Wet Compression Set  2.2 ± 1.16 —  3.6 ± 2.12  8.0 ± 3.51  3.2± 2.02 — @ 50° C., %Conclusions

Reactivity of Novomer polyols in VE formulations was comparable to thereactivity of the reference polyols used in this study. The reactivityof the PU system was not affected significantly after 10% and 20%drop-in replacement of any of commercial polyols used in this studyincluding the cell opening polyol. The reactivity of the PU system wasnot significantly affected after 30% and 45% drop-in replacement ofcommercial polyols with a mixture of the three Novomer polyols. Noadjustment in catalysis was required to obtain open cell foams withNovomer polyols.

VE foams based on Novomer polyols exhibited similar white color to thereference foams. The apparent cell structure of foams with Novomerpolyols was uniform and similar to the reference foams.

Compression Force Deflection (CFD) at 25%, 50%, and 65% deflection of VEfoams was increased by introduction of Novomer polyols. CFD valuesnormalized for the density clearly indicate that foams with Novomerpolyol have higher CFD (better load bearing properties) in comparison tothe reference foams.

Hysteresis Loss, which is independent of foam density, also increasedwith introduction of Novomer polyols which indicates that foams based onNovomer polyols are more energy absorbing than reference VE foams. Allfoams prepared in this study exhibited very low resilience around 1% orless.

The tensile and tear strength of VE foams increased by introduction ofNovomer 58-103-C polyol as replacement for Poly-G 76-120 polyols ofsimilar equivalent weight, with and without calcium carbonate as filler.An increase in tensile strength and tear strength properties isespecially high in foams prepared with a proportional mixture of thethree Novomer polyols at 30% and 45% replacement of the three commercialpolyols.

An increase in isocyanate index from 70 to 80 the tensile strength andtear strength increased in the VE foams based on a mixture of Novomerpolyols.

Elongation at break was much higher than the elongation (% strain) atmaximum load. In order to be consistent, the elongation at maximum loadwas reported as the elongation. Without exception, all VE foamsexhibited elongation higher than 100%.

VE foams prepared with a proportional mixture of the three Novomerpolyols at 30% and 45% levels as replacement for base commercial polyolsexhibited huge increase in the recovery time in comparison to thereference foam. This is consistent with the hysteresis values of thesefoams.

Dray and wet compression set was measured on selected number of VEfoams. In all foams containing up to 30% Novomer polyols based on totalpolyols both dry and wet compression sets were relatively low andcomparable to the reference foam.

Based on DMA measurements it can be concluded that Novomer polyolsimpart improved energy absorbing properties to the VE foam formulationswhich are consistent with the hysteresis loss results. Higher energyabsorption is a desirable characteristic in visco-elastic foams.

Example 3: TDI-Based Seating Foams

Presented below are the formulations and properties of high strengthTDI-based polyurethane foams prepared according to the principles of thepresent invention. These materials were made to evaluate theirsuitability for seating foam applications. The TDI foams were made usingaliphatic polycarbonate polyol additives as defined herein.Specifically, the aliphatic polycarbonate polyols hereinafter alsoreferred to as “Novomer Polyols” used in the formulations below have thefollowing properties:

Polyol Batch No. 58-103-C 74-276 80-148 80-163 Acid Value, mg KOH/g 0.280.51 2.68 2.09 Hydroxyl Value, mg KOH/g 119 61.1 111.7 64.9 Mn (GPC)1,270 2,213 1337 2205 Mw (GPC) 1,370 2,443 1453 2345 Polydispersity,Mw/Mn 1.07 1.06 1.09 1.06 Glass Transition Temp. −5° C. −5.5° C. 6.0° C.−9.9° C. (DSC), Tg

The structures of polyols 58-103-C and 74-276 are shown above inprevious examples.

Polyol 80-163 is a linear 2250 g/mol poly(propylene carbonate) polyolinitiated with 600 g/mol polypropylene glycol (mixture of isomers)having a PDI of 1.05, greater than 99% —OH end groups and greater than99% carbonate linkages (exclusive of the ether bonds in thepolypropylene glycol). This polyol conforms to the formula:

where k is on average about 9, and n is on average in the compositionapproximately 7.

Polyol 80-148 is a linear poly(propylene carbonate) polyol initiatedwith propylene glycol and having an Mn of 1340 g/mol, a PDI of 1.09,greater than 99% —OH end groups and greater than 99% carbonate linkages.This polyol conforms to the formula:

where n is, on average in the composition, approximately 13.

Raw Materials

A list of raw materials used in this evaluation is shown in TablesEx3-1a and Ex3-1b.

All materials were used as received from suppliers including Novomerpolyols.

TABLE Ex3-1a Materials Designation Type Supplier POLYOLS Poly-G 85-29Ethylene oxide caped polyether Arch polyol (triol) Chemicals HydroxylValue = 27.4 mg KOH/g; Eq. wt. = 2047.445 Viscosity @ 25° C. = 1150 cPsVoranol-Voractiv A catalytically Active, High- DOW 6340 functionality EOCaped Polyether Polyol; OH # 32 mg KOH/g; Eq. wt. = 1753.13 Watercontent = 0.031% Speciflex NC-701 Grafted polyether polyol DOWcontaining copolymerized styrene and acrylonitrile Hydroxyl Value = 23.0mg KOH/g; Eq. wt. = 2439.13 Viscosity @ 25° C. = 5070 mPa · s NovomerPPC- Novomer Poly(Propylene Carbonate) NOVOMER 1.2-DPG Hydroxyl Value =119 mg KOH/g; Batch 58-103-C Eq. wt. = 471.43 Acidity Value = 0.28 mgKOH/g Viscosity @ 25° C. = 1.25 × 10⁶ cPs Viscosity @ 80° C. = 4990 cPsNovomer PPC- Novomer Poly(Propylene Carbonate) NOVOMER 1kd-PG HydroxylValue = 111.72 mg KOH/g; Batch 80-148 Eq. wt. = 502.15 Acidity Value =2.68 mg KOH/g Novomer PPC- Novomer Poly(Propylene Carbonate) NOVOMER2kd-PEOL Hydroxyl Value = 64.94 mg KOH/g; Batch 80-163 Eq. wt. = 863.87Acidity Value = 2.09 mg KOH/g Novomer PPC- Novomer Poly(PropyleneCarbonate) NOVOMER 2.3-PEOL Hydroxyl Value = 61.1 mg KOH/g; Batch 74-276Eq. wt. = 918.47

TABLE Ex.3-1b Materials Designation Type Supplier SURFACTANTS Tegostab B4690 Polyether/Silicone Oil Mix Evonik Eq. Wt. = 1335.7 CELL OPENERLumulse POE 26 Hydroxyl Value = 134.8 mg KOH/g Lambent Eq. Wt. = 416.2CHAIN EXTENDERS Diethanolamine Eq. Wt. = 35.04 Aldrich CATALYSTS Dabco33LV 33% Triethylenediamine in Air dipropylene glycol Products Niax A1bis(2-dimethylaminoethyl) ether Momentive ISOCYANATES Lupranate ®  T80Toluene Disocyanate BASF Type 1 Eq.Wt. = 87.54Solubility/Compatibility of Novomer Polyols with Commercial PolyetherPolyols

In foaming experiments, a formulation targeting high resilient flexiblefoams was used as reference. This formulation is based on a mixture ofPoly-G 85-29 ethylene oxide tipped polyether triol (polyol) andVoranol-Voractiv 6340 which is a catalytically active, high functionalEO caped polyether polyol. Speciflex NC-701 was used as graftedpolyether polyol. Lumulse POE 26 (ethoxylated glycerol) was used as areactive cell opener. Diethanol amine was used as a co-catalyst andcross-linker.

Preparation and Testing of Foams

Reference free rise water-blown foams were prepared with 0%, 10%, and20% Speciflex NC-701 graft polyol at 90 Isoctanate Index (Tables Ex3-2to Ex3-5). Reference molded foams were prepared with 0%, 10%, 15%, 20%,and 25% Speciflex NC-701 graft polyol (Tables Ex3-6 to Ex3-10).

Both free-rise and molded foams were prepared with 10% and 20% NovomerPPC-2kd-PEOL polyol (Table Ex3-3 and Ex3-8). At 20% 80-163polyol-containing molded foams were prepared targeting 2.5 and 3.5 pcffoam density (Table 8A).

Due to the limited compatibility with commercial polyols, free-risefoams were prepared with 10% and molded foams with 10% and 15% of polyol80-148 (Table Ex3-5 and Ex3-10). Molded foams containing 15% 80-148polyol were prepared targeting 2.5 and 3.5 pcf foam density (TableEx3-10).

Free-rise foams were prepared with 10%, 12.5% and 26.9% polyol 74-276(Table Ex3-2) and 10%, 12.5% and 16.7% 58-103C polyol (Table Ex3-4).Molded foams were prepared with 10% of each of these two polyols (TablesEx3-7 and Ex3-9) and 20% polyol 74-276 (Table Ex3-7).

In some cases, free-rise and molded foams were prepared with a mixtureof Speciflex NC-701 graft polyether polyol and Novomer polyols (TablesEx3-2 to Ex3-4, Ex3-7, Ex3-8B, and Ex3-9).

Free-rise foams were prepared using a standard laboratory hand-mixingprocedure. Foaming profiles, including cream time, gel time, and risetime were measured on all foams. After the rise time, the foams wereimmediately placed in an air-circulating oven preheated at 80° C. for 30minutes to complete the cure.

Molded foams were prepared using an aluminum mold with 12×12×2 inchdimensions preheated at 70° C. Demolding time was 4.5 minutes.

All foams were aged under room conditions for minimum one week beforetesting. Full evaluation was carried out on molded foams. The followingproperties were measured according to ASTM D 3574-08:

-   -   Foam Density (Test A)    -   Resilience via Ball Rebound (Test H)    -   Tensile Strength at Break (Test E)    -   Elongation at Break (Test E)    -   Tear Strength (Test F)    -   CFD, Compression Force Deflection (Test C)    -   Hysteresis (Procedure B—CFD Hysteresis Loss)    -   Dry Constant Deflection Compression Set (Test D)    -   Wet Constant Deflection Compression Set (Test D & Wet Heat        Aging, Test L)    -   Tensile strength and Elongation after Dry Heat Aging for 22        hours at 140° C. (Modified Heat Aging Test K)

Flammability was measured as Horizontal Burning Rate according to thein-house method, which was modified from ASTM D 5132-04.

IV. RESULTS

Polyol Compatibility

After 24 hours, Novomer PPC-2kd-PEOL polyol was compatible up-to 25%levels with a 50/50 mixture of Poly-G 85-29 polyol and Voranol 6340polyol.

Novomer polyol 80-148 was compatible with a mixture of the twocommercial polyols up to 15% levels immediately after blending. After 24hours, the blend separated into a two phase system.

Polyol Reactivity

Introduction of the four different Novomer polyols into reference foamformulation as drop-in replacement for Poly-G 85-29 and Voranol Voractiv6340 did not significantly affect the reaction profile (foaming profile)measured as cream time, gel time, and rise time (Tables Ex3-2 to Ex3-5).No adjustment in catalyst was need.

Apparent Foam Cell Structure and Density

Free-rise foams based on Novomer polyols exhibited similar white colorto the reference foams prepared with or without graft polyol SpeciflexNC-701. The apparent cell structure of foams with Novomer polyols wasuniform and similar to the reference foams.

Density of the free-rise foams did not change significantly with adrop-in replacement of Poly-G 85-29 and Voranol Voractiv 6340 polyolswith Novomer polyols (Tables Ex3-2 to Ex3-5).

The apparent cell structure of molded foams prepared with Novomerpolyols was uniform and similar to the reference foams prepared with amixture of Poly-G 85-29 and Voranol Voractiv 6340 polyols and referencefoams prepared with graft polyol Speciflex NC-701.

Foam Physical Properties

In this study, free-rise foams were prepared mostly to evaluatereactivity of epoxide-CO₂ based polyols and their effect on foamingprofile. Free-rise TDI foams exhibited significantly higher resiliencein comparison to the MDI-based HR foams prepared at the same levels ofNovomer polyols (Example 1). MDI-Based foams prepared with 10% and 25%Novomer polyol 74-276 exhibited resilience of 49% and 36%, respectively.TDI foams based on 10% and 26.9% of the same polyol exhibited resilienceof 53 and 42%. TDI foams prepared with 10% and 16.7% Novomer polyol58-103 exhibited resilience of 55% and 45%, respectively, and MDI foamsprepared with 10% and 15% of the same polyol exhibited resilience of 43%and 39%.

Reference free-rise foams prepared with a graft polyol (SpeciflexNC-701) also exhibited lower resilience in comparison to the referencefoam prepared with base polyether polyols.

The same effect of the graft polyol and Novomer polyols on theresilience was observed in the molded foams (Tables Ex3-6 to Ex3-10). Inall cases, the resilience of the molded foams somewhat decreased andhysteresis somewhat increased with introduction of the graft polyol andNovomer polyols (Tables Ex3-6 to Ex3-10). However, the resilience wassignificantly higher and hysteresis significantly lower, regardless ofthe type of Novomer polyol (Tables Ex3-6 to Ex3-10), in comparison tothe MDI-based foams at the same levels.

All molded TDI foams based on Novomer polyols exhibited hysteresis lowerthan 35% (Tables 7-10, FIGS. 24 and 25), which is a maximum specified byChrysler Material standard for Type IV foams with a minimum densityrequirement of 2 pcf (32 kg/m³) (FIG. 33), with one exception; the foamwith 20% polyol 74-276 exhibited hysteresis of 35.3% (Table Ex3-7). Thedensity of all molded foams was around 2.4 pcf (38 kg/m³).

Based on hysteresis results, all foams prepared with Novomer polyols canbe classified as High Resilient (HR) PU foams.

In general, the tensile strength increased with introduction of Novomerpolyols. With introduction of Novomer polyol the elongation did notchange significantly (Tables Ex3-7 to Ex3-10). These results indicatethat the foam strength (toughness) increases by introduction of theNovomer polyols.

The tear strength measured on foams prepared with Novomer polyols wassignificantly higher in comparison to the reference foam prepared withthe base polyether polyols Poly-G 85-29 and Voranol Voractiv 6340(Tables Ex3-7 to Ex3-9). The tear strengths of foams based on polyol75-276, 80-163, and 58-103-C polyols were similar in comparison to thereference foams prepared with the graft polyol (Tables Ex3-7 to Ex3-9).These results also indicate that the foam strength (toughness) increasesby introduction of the Novomer polyols.

All molded foams based on Novomer polyols exhibited significantly higherCompression Force Deflection (CFD) at 25%, 50%, and 65% deflections incomparison to the reference foam prepared with the base polyols as solepolyols and similar or slightly higher CFD in comparison to thereference foams based on graft polyol (Tables Ex3-7 to Ex3-10, FIGS.26-31). These results clearly indicate that Novomer polyols improve theload bearing properties of the flexible foams. More importantly, the SAGfactor was not affected significantly by the introduction of Novomerpolyols into foam formulations (Tables Ex3-7 to Ex3-10, FIG. 32).

The dry and wet compression set of molded foams based on Novomer polyolswas somewhat higher in comparison to the reference foams (Tables Ex3-7to Ex3-10). Molded foams prepared with the graft polyol also exhibitedslightly higher compression set values in comparison to the referencefoams prepared with the based polyether polyol (Table Ex3-6). However,all molded foams prepared with Novomer polyols meet the wet compressionset requirements of 25% maximum defined by the Chrysler MaterialStandard for Type IV foams (FIG. 33).

Practically all molded foams based on Novomer polyols met the hysteresisloss, tear resistance, and wet compression requirements of the ChryslerMaterial Standard for Type IV foams.

The flammability of molded foams was not affected by addition of Novomerpolyols. The burning rate of all molded foams based on Novomer polyolswas around 100 mm/min which is in the range of reference foams preparedwith and without the graft polyol (Tables Ex3-6, Ex3-7, Ex3-8A, Ex3-9,and Ex3-10. If needed, the flammability of the foams can easily beadjusted by addition of small amount of flame retardants.

Retention of tensile strength properties was excellent in all measuredfoams after dry aging for 22 hours at 140° C. (Tables Ex3-6, Ex3-7,Ex3-8A, Ex3-9, and Ex3-10). In some cases, the stress-strain propertiesimproved with dry heat aging which was not observed in MDI foams(Example 1). This might be ascribed to the annealing effect underelevated temperature of TDI-based polymer network.

Properties of Foams Prepared with NOVOMER Polyols Targeting Density of3.5 Pcf

The density of the molded foams described above was around 2.4 pcf (˜38kg/m³) which is in a range of Type IV HR foams for seat applicationsaccording to Chrysler Material Standard MS-DC-649 (FIG. 33). Two typesof molded foams were also prepared targeting density of 3.5 pcf (˜56kg/m³). Both foams based on 20% polyol 74-176 (Designation 6B in TableEx3-8A) and 15% polyol 80-148 (Designation 7B in Table Ex3-10) exhibitedhigher CFD properties and higher tensile and tear strength in comparisonto the foams prepared at lower densities. More importantly, both foamsexhibited lower hysteresis loss and lower wet and dry compression set(Tables Ex3-8A and Ex3-10).

TABLE EX3-2 Formulations of Free-Rise Foams Based on Polyol 74-276 Eqv.Designation F Weight 1 2 3 4 5 6 7 Sample Reference R-10%-NC- R-20%-NC-74-276-1 74-276-2 74-276-3 74-276-4 designation (R-9) 701 701 % Novomer-0 0 0 12.5 26.9 10 10 polyol on total polyols % Graft polyol 0 10 20 0 00 10 on total polyols Polyol system Poly-G 85-29 3 2047.5 48.5 38.8 38.848.5 48.5 38.8 38.8 DVV 6340 1753.13 48.5 48.5 38.8 36.37 22.39 48.538.8 Speciflex NC-701 2244 — 9.7 19.4 — — — 9.7 Novomer 918.47 — — —12.126 26.11 9.7 9.7 PPC-2.3-PEOL #74-276 Water 2 9 3.6 3.6 3.6 3.6 3.63.6 3.6 Lumulse POE 26 416.2 3 3 3 3 3 3 3 Teaostab B 4690 1335.7 1 1 11 1 1 1 Dabco 33LV 105 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Diethanolamine 35.041 1 1 1 1 1 1 Niax A-1 233.7 0.05 0.05 0.05 0.05 0.05 0.5 0.5 IsocyanateSystem Lupranate TD80 87.54 38.83 38.79 38.70 39.32 39.89 39.28 38.85Isocyanate Index 90 90 90 90 90 90 90 Reaction Proile of Free-riseNumber of 3 1 1 1 1 1 1 foaming experiments Mix time, sec. 5 5 5 5 5 5 5Cream time. sec. 10 ± 1  9 9 9 8 8 8 Gel time, sec. 47 ± 1  48 51 51 5551 49 Rise time, sec. 79 ± 4  86 77 88 80 79 81 Post-curing time 30 min30 min 30 min 30 min 30 min 30 min 30 min & temperature @ 80° C. @ 80°C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. Properties Free-risedensity, 1.68 ± 0.04 1.64 ± 0.05 1.78 ± 0.04 1.77 ± 0.06 1.88 ± 0.091.75 ± 0.01 1.72 ± 0.02 pcf Resilience, % 66.57 ± 0.7  60.98 ± 2.01 57.16 ± 2.38  53.35 ± 2.38  41.92 ± 1.27  52.85 ± 1.45  55.39 ± 2.13 CFD @ 25%, psi 0.12 ± 0.01 — — — — — — CFD @ 50%, psi 0.19 ± 0.02 — — —— — — CFD @ 65%, psi 0.32 ± 0.03 — — — — — — Comments

TABLE EX3-3 Formulations of Free-Rise Foams Based on Polyol 80-163 Eqv.Designation F Weight 1 2 3 4 5 6 Sample designation Reference R-10%-NC-R-20%-NC- PPC-80-163 PPC-80-163- PPC-80-163 (R-9) 701 701 10% 10%-S 20%% Novomerpolyol 0 0 0 10 10 20 on total polyols % Graft polyol 0 10 20 010 0 on total polyols Polyol system Poly-G 85-29 3 2047.5 48.5 38.8 38.838.8 38.8 29.1 DVV 6340 1753.13 48.5 48.5 38.8 48.5 38.8 48.5 SpeciflexNC-701 2244 — 9.7 19.4 — 9.7 — Novomer PPC-2kd- 863.87 — — — 9.7 9.719.4 PEOL #80-163 Water 2 9 3.6 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26 416.23 3 3 . 3 3 Tegostab B 4690 1335.7 1 1 1 1 1 1 Dabco 33LV 105 0.5 0.50.5 0.5 0.5 0.5 Diethanolamine 35.04 1 1 1 1 1 1 Niax A-1 233.7 0.050.05 0.05 0.05 0.05 0.05 Isocyanate System Lupranate TD80 87.54 38.8338.79 38.70 39.97 39.54 41.12 Isocyanate Index 90 90 90 91 91 93Reaction Profile of Free-rise Number of foaming 3 1 1 1 1 1 experimentsMix time, sec. 5 5 5 5 5 5 Cream time, sec. 10 ± 1  9 9 8 8 8 Gel time,sec. 47 ± 1  48 51 48 49 47 Rise time, sec. 79 ± 4  86 77 81 86 81Post-curing time 30 min 30 min 30 min 30 min 30 min 30 min & temperature@ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. PropertiesFree-rise density, pcf 1.68 ± 0.04 1.64 ± 0.05 1.78 ± 0.04 1.84 ± 0.081.66 ± 0.07 1.70 ± 0.06 Resilience, % 66.57 ± 0.7  60.98 ± 2.01  57.16 ±2.38  60.47 ± 1.45  57.67 ± 1.14  47.51 ± 1.14  CFD @ 25%, psi 0.12 ±0.01 — — — — — CFD @ 50%, psi 0.19 ± 0.02 — — — — — CFD @ 65%, psi 0.32± 0.03 — — — — — Comments

TABLE EX3-4 Formulations of Free-RiseFoams Based on Polyol 58-103-C Eqv.Designation F Weight 1 2 3 4 5 6 7 Sample designation ReferenceR-10%-NC- R-20%-NC- 58-103-C-1 58-103-C-2 58-103-C-3 58-103-C-4 (R-9)701 701 % Novomerpolyol 0 0 0 12.5 16.7 10 10 on total polyols % Graftpolyol 0 10 20 0 0 0 10 on total polyols Polyol system Poly-G 85-29 32047.5 48.5 38.8 38.8 48.5 48.5 38.8 38.8 DVV 6340 1753.13 48.5 48.538.8 36.37 32.33 48.5 38.8 Speciflex NC-701 2244 — 9.7 19.4 — — — 9.7Novomer PPC-1.2- 471.43 — — — 12.13 16.17 9.7 9.7 DPG #58-103 Water 2 93.6 3.6 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26 416.2 3 3 3 3 3 3 3 TegostabB 4690 1335.7 1 1 1 1 1 1 1 Dabco 33LV 105 0.5 0.5 0.5 0.5 0.5 0.5 0.5Diethanolamine 35.04 1 1 1 1 1 1 1 Niax A-1 233.7 0.05 0.05 0.05 0.050.05 0.05 0.05 Isocyanate System Lupranate TD80 87.54 38.83 38.79 38.7039.32 40.80 40.07 39.64 Isocyanate Index 90 90 90 90 90 90 90 ReactionProfile of Free-rise Number of foaming 3 1 1 1 1 1 1 experiments Mixtime, sec. 5 5 5 5 5 5 5 Cream time, sec. 10 ± 1  9 9 9 8 9 9 Gel time,sec. 47 ± 1  48 51 50 53 52 49 Rise time, sec. 79 ± 4  86 77 83 91 85 81Post-curing time 30 min 30 min 30 min 30 min 30 min 30 min 30 min &temperature @ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80° C. @ 80°C. Properties Free-rise density, 1.68 ± 0.04 1.64 ± 0.05 1.78 ± 0.04 1.74 ± 0.05 1.74 ± 0.08 1.70 ± 0.03 1.66 ± 0.04 pcf Resilience, % 66.57± 0.7  60.98 ± 2.01  57.16 ± 2.38  49.29 ± 1.06 44.72 ± 1.06  54.62 ±2.01  52.59 ± 1.70  CFD @ 25%, psi 0.12 ± 0.01 — — — — — — CFD @ 50%,psi 0.19 ± 0.02 — — — — — — CFD @ 65%, psi 0.32 ± 0.03 — — — — — —Comments

TABLE EX3-5 Formulations of Free-Rise Foams Based on Polyol 80-148 Eqv.Designation F Weight 1 2 3 4 5 6 7 Sample designation Reference (R-9)R-10%-NC-701 R-20%-NC-701 PPC-80-148 % Novomerpolyol on total polyols 00 0 10 % Graft polyol on total polyols 0 10 20 0 Polyol system Poly-G85-29 3 2047.5 48.5 38.8 38.8 38.8 DVV 6340 1753.13 48.5 48.5 38.8 48.5Speciflex NC-701 2244 — 9.7 19.4 — Novomer PPC-1kd-PG #80-148 502.15 — —— 9.7 Water 2 9 3.6 3.6 3.6 3.6 Lumulse POE 26 416.2 3 3 3 3 Tegostab B4690 1335.7 1 1 1 1 Dabco 33LV 105 0.5 0.5 0.5 0.5 Diethanolamine 35.041 1 1 1 Niax A-1 233.7 0.05 0.05 0.05 0.05 Isocyanate System LupranateTD80 87.54 38.83 38.79 38.70 39.34 Isocyanate Index 90 90 90 89 ReactionProfile of Free-rise Number of foaming experiments 3 1 1 1 Mix time,sec. 5 5 5 5 Cream time, sec. 10 ± 1  9 9 8 Gel time, sec. 47 ± 1  48 5148 Rise time, sec. 79 ± 4  86 77 82 Post-curing time & temperature 30min 30 min 30 min 30 min @ 80° C. @ 80° C. @ 80° C. @ 80° C. PropertiesFree-rise density, pcf 1.68 ± 0.04 1.64 ± 0.05 1.78 ± 0.04 1.70 ± 0.04Resilience, % 66.57 ± 0.7  60.98 ± 2.01  57.16 ± 2.38  56.66 ± 1.70  CFD@ 25%, psi 0.12 ± 0.01 — — — CFD @ 50%, psi 0.19 ± 0.02 — — — CFD @ 65%,psi 0.32 ± 0.03 — — — Comments

TABLE EX3-6 Formulations of Molded Reference Foams and Foams Based onGraft Polyol Eqv. Designation F Weight 1 2 3 4 5 Sample designation Ref.(R-9) R-10%-NC-701 R-15%-NC-701 R-20%-NC-701 R-25%-NC-701 %Novomerpolyol on total polyols 0 0 0 0 0 % Graft polyol on total polyols0 10 15 20 25 Polyol system Poly-G 85-29 3 2047.5 48.5 38.8 41.23 38.836.38 DVV 6340 1753.13 48.5 48.5 41.23 38.8 36.38 Speciflex NC-701 2244— 9.7 14.55 19.4 24.25 Water 2 9 3.6 3.6 3.6 3.6 3.6 Lumulse POE 26416.2 3 3 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 1 Dabco 33LV 105 0.5 0.50.5 0.5 0.5 Diethanolamine 35.04 1 1 1 1 1 Niax A-1 233.7 0.05 0.05 0.050.05 0.05 Isocyanate System Lupranate TD80 87.54 38.83 38.79 38.22 38.7038.67 Isocyanate Index 90 90 90 90 90 Reaction Profile of Free-rise Mixtime, sec. 5 5 5 5 5 Component temperature, ° C. RT RT RT RT RTDemolding time, sec. 270 270 270 270 270 Mold temperature, ° C. 70 70 7070 70 Properties Density, pcf  2.39 ± 0.02 2.43 ± 0   2.49 ± 0.03  2.36± 0.03 2.37 ± 0.03 Resilience, % 66.06 ± 0.90 63.77 ± 2.09 63.26 ± 0.57 59.20 ± 2.31 59.96 ± 1.66  CFD @ 25%, psi 0.30 ± 0    0.36 ± 0.01 0.42 ±0.02  0.41 ± 0.01 0.47 ± 0.01 CFD @ 50%, psi  0.42 ± 0.01  0.51 ± 0.020.58 ± 0.03  0.58 ± 0.02 0.67 ± 0.01 CFD @ 65%, psi  0.64 ± 0.02  0.79 ±0.04 0.87 ± 0.06  0.87 ± 0.05 1.00 ± 0.05 Hysteresis, % 20.17 ± 0.5421.75 ± 0.13 22.46 ± 0.37  24.06 ± 0.20 — Wet Compression, % 12.1 ± 0.616.1 ± 1.5 15.8 ± 0.9  15.4 ± 0.7 20.0 ± 1.2  Dry Compression, % 5.8 ±0   7.6 ± 1.2 5.8 ± 0.8  7.2 ± 1.5 6.4 ± 1.7 Tensile Strength, psi 12.57± 1.30 16.07 ± 0.73 — 18.28 ± 1.77 — Elongation at Break, % 142 ± 14 143± 7  — 142 ± 10 — Tear Strength, N/m 605.9 ± 49.8 741.2 ± 41.9 — 898.2 ±78.3 — Burning Rate, mm/min 103 ± 5  — — 98 ± 3 — Tensile Strength afterDry Heat Aging, psi 20 ± 1 — — 25 ± 2 — Elongation Strength after DryHeat Aging, % 244 ± 4  — — 210 ± 16 — Comments

TABLE EX3-7 Formulations of Reference and Molded Foams Based on Polyol74-276 Eqv. Designation F Weight 1 2 3 4 5 6 Sample designation Ref.R-10%-NC- R-20%-NC- 74-276-3 74-276-4 74-276-7 (R-9) 701 701 %Novomerpolyol on total polyols 0 0 0 10 10 20 % Graft polyol on totalpolyols 0 10 20 0 10 0 Polyol system Poly-G 85-29 3 2047.5 48.5 38.838.8 38.8 38.8 38.8 DVV 6340 1753.13 48.5 48.5 38.8 48.5 38.8 38.8Speciflex NC-701 2244 — 9.7 19.4 — 9.7 — Novomer PPC-2.3-PEOL #74-276918.47 — — — 9.7 9.7 19.4 Water 2 9 3.6 3.6 3.6 3.6 3.6 3.6 Lumulse POE26 416.2 3 3 3 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 1 1 Dabco 33LV 1050.5 0.5 0.5 0.5 0.5 0.5 Diethanolamine 35.04 1 1 1 1 1 1 Niax A-1 233.70.05 0.05 0.05 0.5 0.5 0.5 Isocyanate System Lupranate TD80 87.54 38.8338.79 38.70 39.28 38.85 39.68 Isocyanate Index 90 90 90 90 90 90Reaction Profile of Free-rise Mix time, sec. 5 5 5 5 5 5 Componenttemperature, ° C. RT RT RT RT RT RT Demolding time, sec. 270 270 270 270270 270 Mold temperature, ° C. 70 70 70 70 70 70 Properties Density, pcf 2.39 ± 0.02 2.43 ± 0    2.36 ± 0.03  2.44 ± 0.05 2.44 ± 0.04  2.53 ±0.03 Resilience, % 66.06 ± 0.90 63.77 ± 2.09 59.20 ± 2.31 58.43 ± 0.9056.40 ± 1.93  52.85 ± 0.70 CFD @ 25%, psi 0.30 ± 0    0.36 ± 0.01  0.41± 0.01  0.35 ± 0.01 0.42 ± 0.01  0.49 ± 0.02 CFD @ 50%, psi  0.42 ± 0.01 0.51 ± 0.02  0.58 ± 0.02  0.50 ± 0.01 0.60 ± 0.01  0.68 ± 0.02 CFD @65%, psi  0.64 ± 0.02  0.79 ± 0.04  0.87 ± 0.05  0.73 ± 0.03 0.92 ± 0.04 0.97 ± 0.05 Hysteresis, % 20.17 ± 0.54 21.75 ± 0.13 24.06 ± 0.20 26.17± 0.99 27.98 ± 0.88  35.32 ± 0.26 Wet Compression, % 12.1 ± 0.6 16.1 ±1.5 15.4 ± 0.7 17.9 ± 1.1 24.4 ± 0.9  24.9 ± 1.1 Dry Compression, % 5.8± 0   7.6 ± 1.2  7.2 ± 1.5  7.2 ± 2.1 6.6 ± 1.2  7.9 ± 0.4 TensileStrength, psi 12.57 ± 1.30 16.07 ± 0.73 18.28 ± 1.77 15.53 ± 1.06 —15.99 ± 2.28 Elongation at Break, % 142 ± 14 143 ± 7  142 ± 10 149 ± 9 — 165 ± 12 Tear Strength, N/m 605.9 ± 49.8 741.2 ± 41.9 898.2 ± 78.3749.8 ± 65.2 — 838.5 ± 65.4 Burning Rate, mm/min — — — — — 96 ± 4Tensile Strength after Dry Heat Aging, psi — — — — — 15.7 ± 0.9Elongation Strength after Dry Heat Aging, % — — — — — 187 ± 1  Comments

TABLE EX3-8A Formulations of reference and Molded Foams Based on Polyol80-163 6B Target Designation 1 2 3 4 5 6A higher density 7 Sampledesignation Ref. R-10%-NC- R-20%-NC- R-25%-NC- PPC-80-163- PPC-80-163-PPC-80-163- PPC-80-163- (R-9) 701 701 701 10%-90II 20% 20% 25% %Novomerpolyol 0 0 0 0 10 20 20 25 on total polyols % Graft polyol 0 1020 25 0 0 0 0 on total polyols Polyol system Poly-G 85-29 48.5 38.8 38.836.38 38.8 38.8 38.8 36.38 DVV 6340 48.5 48.5 38.8 36.38 48.5 38.8 38.836.38 Speciflex NC-701 — 9.7 19.4 24.25 — — — — Novomer PPC-2kd- — — — —9.7 19.4 19.4 24.25 PEOL #80-163 Water 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6Lumulse POE 26 3 3 3 3 3 3 3 3 Tegostab B 4690 1 1 1 1 1 1 1 1 Dabco33LV 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Diethanolamine 1 1 1 1 1 1 1 1 NiaxA-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Isocyanate System LupranateTD80 38.83 38.79 38.70 38.67 39.34 39.79 39.79 40.03 Isocyanate Index 9090 90 90 90 90 90 90 Reaction Profile of Free-rise Mix time. sec. 5 5 55 5 5 5 5 Component RT RT RT RT RT RT RT RT temperature, ° C. Demoldingtime, sec. 270 270 270 270 270 270 270 270 Mold temperature, ° C. 70 7070 70 70 70 70 70 Properties Density, pcf  2.39 ± 0.02 2.43 ± 0    2.36± 0.03 2.37 ± 0.03  2.46 ± 0.03  2.53 ± 0.08 3.52 ± 0.08 2.37 ± 0.07Resilience, % 66.06 ± 0.90 63.77 ± 2.09 59.20 ± 2.31 59.96 ± 1.66  59.71± 1.27 53.61 ± 1.06 44.21 ± 2.44  — CFD @ 25%, psi 0.30 ± 0    0.36 ±0.01  0.41 ± 0.01 0.47 ± 0.01  0.42 ± 0.02  0.42 ± 0.01 0.83 ± 0.03 —CFD @ 50%, psi  0.42 ± 0.01  0.51 ± 0.02  0.58 ± 0.02 0.67 ± 0.01  0.58± 0.03  0.61 ± 0.01 1.16 ± 0.04 — CFD @ 65%, psi  0.64 ± 0.02  0.79 ±0.04  0.87 ± 0.05 1.00 ± 0.05  0.85 ± 0.07  0.93 ± 0.01 1.74 ± 0.11 —Hysteresis, % 20.17 ± 0.54 21.75 ± 0.13 24.06 ± 0.20 — 26.49 ± 0.6933.07 ± 0.68 27.15 ± 2.36  — Wet Compression, % 12.1 ± 0.6 16.1 ± 1.515.4 ± 0.7 20.0 ± 1.2  20.1 ± 0.5 24.8 ± 1.3 20.2 ± 2.1  — DryCompression, % 5.8 ± 0   7.6 ± 1.2  7.2 ± 1.5 6.4 ± 1.7  6.8 ± 1.9  9.1± 1.3 7.9 ± 1.3 — Tensile Strength, psi 12.57 ± 1.30 16.07 ± 0.73 18.28± 1.77 — 16.92 ± 1.11 15.54 ± 0.69 26.34 ± 1.29  — Elongation at Break,% 142 ± 14 143 ± 7  142 ± 10 — 141 ± 9  158 ± 19 152.24 ± 5.56  — TearStrength, N/m 605.9 ± 49.8 741.2 ± 41.9 898.2 ± 78.3 — 829.0 ± 76.0877.7 ± 36.2 1231.0 ± 106.7  — Burning Rate, mm/min — — — — — 98 ± 5 97± 11 — Tensile Strength after 14.3 ± 0.9 29.65 ± 2.07  Dry Heat Aging,psi Elongation Strength 184 ± 14 252.75 ± 7.20  after Dry Heat Aging, %Comments Coarse

TABLE EX3-8B Formulations of Reference and Molded Foams Based on Polyol80-163 Eqv. Designation F Weight 1 2 3 4 Sample designation Ref. (R-9)R-10%-NC-701 PPC-80-163-10% PPC-80-163-10%-S % Novomerpolyol on totalpolyols 0 0 10 10 % Graft polyol on total polyols 0 10 0 10 Polyolsystem Poly-G 85-29 3 2047.5 48.5 38.8 38.8 38.8 DVV 6340 1753.13 48.548.5 48.5 38.8 Speciflex NC-701 2244 — 9.7 — 9.7 Novomer PPC-2kd-PEOL#80-163 863.87 — — 9.7 9.7 Water 2 9 3.6 3.6 3.6 3.6 Lumulse POE 26416.2 3 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 Dabco 33LV 105 0.5 0.5 0.56.5 Diethanolamine 35.04 1 1 1 1 Niax A-1 233.7 0.05 0.05 0.05 0.05Isocyanate System Lupranate TD80 87.54 38.83 38.79 39.97 39.54Isocyanate Index 90 90 91 91 Reaction Profile of Free-rise Number offoaming experiments 2 2 2 2 Mix time, sec. 5 5 5 5 Componenttemperature, ° C. RT RT RT RT Demolding time, sec. 270 270 270 270 Moldtemperature, ° C. 70 70 70 70 Properties Density, pcf  2.39 ± 0.02 2.43± 0   2.36 ± 0.03 2.38 ± 0.04 Resilience, % 66.06 ± 0.90 63.77 ± 2.0958.43 ± 2.69  55.89 ± 2.01  CFD @ 25%, psi 0.30 ± 0    0.36 ± 0.01 0.37± 0.01 0.41 ± 0.01 CFD @ 50%, psi  0.42 ± 0.01  0.51 ± 0.02 0.54 ± 0.010.59 ± 0.01 CFD @ 65%, psi  0.64 ± 0.02  0.79 ± 0.04 0.82 ± 0.03 0.92 ±0.03 Hysteresis, % 20.17 ± 0.54 21.75 ± 0.13 27.10 ± 0.29  28.04 ± 0.73 Wet Compression, % 12.1 ± 0.6 16.1 ± 1.5 16.4 ± 1.1  19.6 ± 1.4  DryCompression, % 5.8 ± 0   7.6 ± 1.2 7.9 ± 2.4 6.6 ± 1.4 Tensile Strength,psi 12.57 ± 1.30 16.07 ± 0.73 — — Elongation at Break, % 142 ± 14 143 ±7  — — Tear Strength, N/m 605.9 ± 49.8 741.2 ± 41.9 — — Comments

TABLE EX3-9 Formulations of Reference and Molded Foams Based on Polyol58-103C Eqv. Designation F Weight 1 2 3 4 5 Sample designation Ref.(R-9) R-10%-NC-701 R-20%-NC-701 58-103-C-3 58-103-C-4 % Novomerpolyol ontotal polyols 0 0 0 10 10 % Graft polyol on total polyols 0 10 20 0 10Polyol system Poly-G 85-29 3 2047.5 48.5 38.8 38.8 38.8 38.8 DVV 63401753.13 48.5 48.5 38.8 48.5 38.8 Speciflex NC-701 2244 — 9.7 19.4 — 9.7Novomer PPC-1.2-DPG #58-103 471.43 — — — 9.7 9.7 Water 2 9 3.6 3.6 3.63.6 3.6 Lumulse POE 26 416.2 3 3 3 3 3 Tegostab B 4690 1335.7 1 1 1 1 1Dabco 33LV 105 0.5 0.5 0.5 0.5 0.5 Diethanolamine 35.04 1 1 1 1 1 NiaxA-1 233.7 0.05 0.05 0.05 0.05 0.05 Isocyanate System Lupranate TD8087.54 38.83 38.79 38.70 40.07 39.64 Isocyanate Index 90 90 90 90 90Reaction Profile of Free-rise Number of foaming experiments 2 2 2 2 2Mix time, sec. 5 5 5 5 5 Component temperature, ° C. RT RT RT RT RTDemolding time, sec. 270 270 270 270 270 Mold temperature, ° C. 70 70 7070 70 Properties Density, pcf  2.39 ± 0.02 2.43 ± 0    2.36 ± 0.03  2.58± 0.03 2.42 ± 0.05 Resilience, % 66.06 ± 0.90 63.77 ± 2.09 59.20 ± 2.3155.64 ± 1.39 51.83 ± 1.06  CFD @ 25%, psi 0.30 ± 0    0.36 ± 0.01  0.41± 0.01  0.36 ± 0.01 0.44 ± 0.02 CFD @ 50%, psi  0.42 ± 0.01  0.51 ± 0.02 0.58 ± 0.02  0.52 ± 0.02 0.63 ± 0.01 CFD @ 65%, psi  0.64 ± 0.02  0.79± 0.04  0.87 ± 0.05  0.79 ± 0.04 0.95 ± 0.04 Hysteresis, % 20.17 ± 0.5421.75 ± 0.13 24.06 ± 0.20 27.34 ± 0.71 30.40 ± 0.76  Wet Compression, %12.1 ± 0.6 16.1 ± 1.5 15.4 ± 0.7 22.1 ± 1.4 24.2 ± 0.8  Dry Compression,% 5.8 ± 0   7.6 ± 1.2  7.2 ± 1.5  9.1 ± 1.8 8.9 ± 0.5 Tensile Strength,psi 12.57 ± 1.30 16.07 ± 0.73 18.28 ± 1.77 15.50 ± 1.89 — Elongation atBreak, % 142 ± 14 143 ± 7  142 ± 10 165 ± 17 — Tear Strength, N/m 605.9± 49.8 741.2 ± 41.9 898.2 ± 78.3 898.7 ± 68.0 — Burning Rate, mm · min —— — 102 ± 5  Tensile Strength after Dry Heat Aging, psi 26.4 ± 1.1Elongation Strength after Dry Heat Aging, % 265 ± 23 Comments

TABLE EX3-10 Formulations of Reference and Molded Foams Based on Polyol80-148 7B Target Designation 1 2 3 4 5 6 7A Higher Density Sampledesignation Ref. R-10%-NC- R-15%-NC- R-20%-NC- PPC-1kd-PG- PPC-80-148-PPC-80-148 PPC-80-148 (R-9) 701 701 701 10% 10%-90II 15% 15% %Novomerpolyol 0 0 0 0 10 10 15 15 on total polyols % Graft polyol 0 1015 20 0 0 0 6 on total polyols Polyol system — Poly-G 85-29 48.5 38.841.23 38.8 38.8 38.8 41.23 41.23 DVV 6340 48.5 48.5 41.23 38.8 48.5 48.541.23 41.23 Speciflex NC-701 — 9.7 14.55 19.4 — — — — Novomer PPC-1kd- —— — — 9.7 9.7 14.55 14.55 PG #80-148 Water 3.6 3.6 3.6 3.6 3.6 3.6 3.63.6 Lumulse POE 26 3 3 3 3 3 3 3 3 Tegostab B 4690 1 1 1 1 1 1 1 1 Dabco33LV 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Diethanolamine 1 1 1 1 1 1 1 1 NiaxA-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Isocyanate System LupranateTD80 38.83 38.79 38.22 38.70 39.34 39.97 40.50 40.50 Isocyanate Index 9090 90 90 89 90 90 90 Reaction Profile of Free-rise Number of foaming 2 21 2 1 1 1 1 experiments Mix time, sec. 5 5 5 5 5 5 5 5 Component RT RTRT RT RT RT RT RT temperature, ° C. Demolding time, sec. 270 270 270 270270 270 270 270 Mold temperature, ° C. 70 70 70 70 70 70 70 70Properties Density, pcf  2.39 ± 0.02 2.43 ± 0   2.49 ± 0.03  2.36 ± 0.03 2.45 ± 0.03  2.50 ± 0.04  2.49 ± 0.05  3.60 ± 0.01 Resilience, % 66.06± 0.90 63.77 ± 2.09 63.26 ± 0.57  59.20 ± 2.31 56.15 ± 1.66 55.13 ± 1.4551.83 ± 1.06 49.03 ± 1.70 CFD @ 25%, psi 0.30 ± 0    0.36 ± 0.01 0.42 ±0.02  0.41 ± 0.01  0.40 ± 0.02  0.44 ± 0.01  0.55 ± 0.02  1.03 ± 0.03CFD @ 50%, psi  0.42 ± 0.01  0.51 ± 0.02 0.58 ± 0.03  0.58 ± 0.02  0.57± 0.02  0.61 ± 0.01  0.78 ± 0.03  1.43 ± 0.04 CFD @ 65%, psi  0.64 ±0.02  0.79 ± 0.04 0.87 ± 0.06  0.87 ± 0.05  0.86 ± 0.06  0.90 ± 0.04 1.16 ± 0.06  2.06 ± 0.07 Hysteresis, % 20.17 ± 0.54 21.75 ± 0.13 22.46± 0.37  24.06 ± 0.20 27.69 ± 0.29 29.08 ± 0.15 32.28 ± 0.38 29.37 ± 6.42Wet Compression, % 12.1 ± 0.6 16.1 ± 1.5 15.8 ± 0.9  15.4 ± 0.7 20.8 ±0.7 24.1 ± 1.5 22.6 ± 2.1 18.2 ± 3.6 Dry Compression, % 5.8 ± 0   7.6 ±1.2 5.8 ± 0.8  7.2 ± 1.5 10.8 ± 0.8  8.8 ± 0.3  8.9 ± 0.3  5.2 ± 0.4Tensile Strength, psi 12.57 ± 1.30 16.07 ± 0.73 — 18.28 ± 1.77 — 14.47 ±1.01 13.29 ± 1.43 14.78 ± 2.17 Elongation at Break, % 142 ± 14 143 ± 7 — 142 ± 10 — 160 ± 24 109 ± 14  96 ± 22 Tear Strength, N/m 605.9 ± 49.8741.2 ± 41.9 — 898.2 ± 78.3 — 699.0 ± 37.8 619.7 ± 74.4 811.7 ± 49.9Burning Rate, mm/min — — — — — — 110 ± 5  104 ± 9  Tensile Strengthafter 13.0 ± 0.4 19.16 ± 1.90 Dry Heat Aging, psi Elongation Strength159 ± 9  172.17 ± 24.13 after Dry Heat Aging, %

V. CONCLUSIONS

Introduction of the four different Novomer polyols into reference foamformulation as drop-in replacement for Poly-G 85-29 and Voranol Voractiv6340 did not significantly affect the reaction profile (foaming profile)measured as cream time, gel time, and rise time.

The density and apparent cell structure of the free-rise foams did notchange significantly with a drop-in replacement of Poly-G 85-29 andVoranol Voractiv 6340 polyols with Novomer polyols.

The apparent cell structure of molded foams prepared with Novomerpolyols was uniform and similar to the reference foams prepared with andwithout the graft polyol.

All foams prepared with Novomer polyols exhibited relatively highresilience and relatively low hysteresis loss and thus can be classifiedas High Resilient (HR) PU foams.

The tensile strength and tear strength properties of foams prepared withNovomer polyols were somewhat better in comparison to the referencefoams.

Results of CFD measurements clearly indicate an increase in load bearingproperties of molded foams based on Novomer polyols without significanteffect on the SAG (comfort) factor.

Foams based on Novomer polyols exhibited some increase in wet and drycompression set in comparison to the reference foams. However, allmolded foams prepared with Novomer polyols met the wet compression setrequirements of 25% maximum defined by the Chrysler Material Standardfor Type IV foams.

Practically all molded foams based on Novomer polyols met the hysteresisloss, tear resistance, and wet compression requirements specified by theChrysler Material Standard: MS-DC-649 for “Cellular, Molded PolyurethaneHigh Resilient (HR) Type Seat Applications” (FIG. 33).

The flammability of molded foams was not affected by addition of Novomerpolyols.

Other Embodiments

The foregoing has been a description of certain non-limiting embodimentsof the invention. Accordingly, it is to be understood that theembodiments of the invention herein described are merely illustrative ofthe application of the principles of the invention. Reference herein todetails of the illustrated embodiments is not intended to limit thescope of the claims, which themselves recite those features regarded asessential to the invention.

APPENDIX A ALIPHATIC POLYCARBONATE POLYOLS

This section describes some of the aliphatic polycarbonate polyols thathave utility in methods and compositions of the present invention.Aliphatic polycarbonate polyols referred to herein are derived from thecopolymerization of one or more epoxides and carbon dioxide. Examples ofsuitable polyols, as well as methods of making them are disclosed in PCTpublication WO2010/028362 the entirety of which is incorporated hereinby reference.

It is advantageous for many of the embodiments described herein that thealiphatic polycarbonate polyols used have a high percentage of reactiveend groups. Such reactive end-groups are typically hydroxyl groups, butother reactive functional groups may be present if the polyols aretreated to modify the chemistry of the end groups. Such modifiedmaterials may terminate in amino groups, thiol groups, alkene groups,carboxylate groups, silanes, phosphate derivatives, isocyanate groupsand the like. For purposes of this invention, the term ‘aliphaticpolycarbonate polyol’ typically refers to —OH terminated materials, butthe incorporation of end-group modified compositions is not excluded,unless otherwise specified.

In certain embodiments, at least 90% of the end groups of thepolycarbonate polyol used are reactive groups. In certain embodiments,at least 95%, at least 96%, at least 97% or at least 98% of the endgroups of the polycarbonate polyol used are reactive groups. In certainembodiments, more than 99%, more than 99.5%, more than 99.7%, or morethan 99.8% of the end groups of the polycarbonate polyol used arereactive groups. In certain embodiments, more than 99.9% of the endgroups of the polycarbonate polyol used are reactive groups.

In certain embodiments, at least 90% of the end groups of thepolycarbonate polyol used are —OH groups. In certain embodiments, atleast 95%, at least 96%, at least 97% or at least 98% of the end groupsof the polycarbonate polyol used are —OH groups. In certain embodiments,more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% ofthe end groups of the polycarbonate polyol used are —OH groups. Incertain embodiments, more than 99.9% of the end groups of thepolycarbonate polyol used are —OH groups.

Another way of expressing the —OH end-group content of a polyolcomposition is by reporting its OH# which is measured using methods wellknown in the art. In certain embodiments, the aliphatic polycarbonatepolyols utilized in the present invention have an OH# greater than about40. In certain embodiments, the aliphatic polycarbonate polyols have anOH# greater than about 50, greater than about 75, greater than about100, or greater than about 120.

In certain embodiments, it is advantageous if the aliphaticpolycarbonate polyol compositions have a substantial proportion ofprimary hydroxyl end groups. These are the norm for compositionscomprising poly(ethylene carbonate), but for polyols derivedcopolymerization of substituted epoxides, it is common for some or mostof the chain ends to consist of secondary hydroxyl groups.Poly(propylene carbonate) polyol is one example of a polyol that mayhave mostly secondary hydroxyl end groups. In certain embodiments, suchpolyols are treated to increase the proportion of primary —OH endgroups. This may be accomplished by methods known in the art such as byreacting the secondary hydroxyl groups with reagents such as ethyleneoxide, reactive lactones, and the like. In certain embodiments, thealiphatic polycarbonate polyols are treated with beta lactones,caprolactone and the like to introduce primary hydroxyl end groups. Incertain embodiments, the aliphatic polycarbonate polyols are treatedwith ethylene oxide to introduce primary hydroxyl end groups.

In certain embodiments, polycarbonate polyols with utility for thepresent invention contain a primary repeating unit having a structure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

In certain embodiments, polycarbonate polyols with utility for thepresent invention contain a primary repeating unit having a structure:

where R¹ is as defined above and in the classes, subclasses and examplesherein.

In certain embodiments, aliphatic polycarbonate chains comprise acopolymer of carbon dioxide and ethylene oxide. In certain embodiments,aliphatic polycarbonate chains comprise a copolymer of carbon dioxideand propylene oxide. In certain embodiments, aliphatic polycarbonatechains comprise a copolymer of carbon dioxide and cyclohexene oxide. Incertain embodiments, aliphatic polycarbonate chains comprise a copolymerof carbon dioxide and cyclopentene oxide. In certain embodiments,aliphatic polycarbonate chains comprise a copolymer of carbon dioxideand 3-vinyl cyclohexane oxide.

In certain embodiments, aliphatic polycarbonate chains comprise aterpolymer of carbon dioxide and ethylene oxide along with one or moreadditional epoxides selected from the group consisting of propyleneoxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers,styrene oxides, and epoxides of higher alpha olefins. In certainembodiments, such terpolymers contain a majority of repeat units derivedfrom ethylene oxide with lesser amounts of repeat units derived from oneor more additional epoxides. In certain embodiments, terpolymers containabout 50% to about 99.5% ethylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than about 60% ethyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 75% ethylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 80% ethylene oxide-derivedrepeat units. In certain embodiments, terpolymers contain greater than85% ethylene oxide-derived repeat units. In certain embodiments,terpolymers contain greater than 90% ethylene oxide-derived repeatunits. In certain embodiments, terpolymers contain greater than 95%ethylene oxide-derived repeat units.

In some embodiments, aliphatic polycarbonate chains comprise a copolymerof carbon dioxide and propylene oxide along with one or more additionalepoxides selected from the group consisting of ethylene oxide,1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers,styrene oxides, and epoxides of higher alpha olefins. In certainembodiments, such terpolymers contain a majority of repeat units derivedfrom propylene oxide with lesser amounts of repeat units derived fromone or more additional epoxides. In certain embodiments, terpolymerscontain about 50% to about 99.5% propylene oxide-derived repeat units.In certain embodiments, terpolymers contain greater than 60% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 75% propylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 80% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 85% propylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 90% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 95% propylene oxide-derived repeat units.

In certain embodiments, aliphatic polycarbonate compositions withutility in the present invention have a number average molecular weight(M_(n)) in the range of about 500 g/mol to about 25,000 g/mol.

In certain embodiments, aliphatic polycarbonate chains have an M_(n)less than about 25,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) less than about 10,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n) lessthan about 5,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 500 g/mol and about 15,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 500 g/mol and about 10,000 g/mol. In certain embodiments,aliphatic polycarbonate chains have an M_(n) between about 500 g/mol andabout 5,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 500 g/mol and about 3,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 500 g/mol and about 2,500 g/mol. In certain embodiments,aliphatic polycarbonate chains have an M_(n) between about 500 g/mol andabout 2,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 500 g/mol and about 1,500 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 500 g/mol and about 1,000 g/mol. In certain embodiments,aliphatic polycarbonate chains have an M_(n) between about 1,000 g/moland about 5,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 1,000 g/mol and about 3,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 5,000 g/mol and about 10,000 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 5,000g/mol. In certain embodiments, aliphatic polycarbonate chains have anM_(n) of about 4,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) of about 3,000 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 2,500g/mol. In certain embodiments, aliphatic polycarbonate chains have anM_(n) of about 2,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) of about 1,500 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 1,000g/mol. In certain embodiments, aliphatic polycarbonate chains have anM_(n) of about 850 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) of about 750 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 500g/mol.

In certain embodiments, the aliphatic polycarbonate polyols used arecharacterized in that they have a narrow molecular weight distribution.This can be indicated by the polydispersity indices (PDI) of thealiphatic polycarbonate polymers. In certain embodiments, aliphaticpolycarbonate compositions have a PDI less than 2. In certainembodiments, aliphatic polycarbonate compositions have a PDI less than1.8. In certain embodiments, aliphatic polycarbonate compositions have aPDI less than 1.5. In certain embodiments, aliphatic polycarbonatecompositions have a PDI less than 1.4. In certain embodiments, aliphaticpolycarbonate compositions have a PDI between about 1.0 and 1.2. Incertain embodiments, aliphatic polycarbonate compositions have a PDIbetween about 1.0 and 1.1.

In certain embodiments aliphatic polycarbonate compositions of thepresent invention comprise substantially alternating polymers containinga high percentage of carbonate linkages and a low content of etherlinkages. In certain embodiments, aliphatic polycarbonate compositionsof the present invention are characterized in that, on average in thecomposition, the percentage of carbonate linkages is 85% or greater. Incertain embodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 90% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 91% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 92% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 93% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 94% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 95% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 96% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 97% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 98% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 99% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 99.5% or greater. In certainembodiments, the percentages above exclude ether linkages present inpolymerization initiators or chain transfer agents and refer only to thelinkages formed during epoxide CO₂ copolymerization.

In certain embodiments, aliphatic polycarbonate compositions of thepresent invention are characterized in that they contain essentially noether linkages either within the polymer chains derived from epoxide CO₂copolymerization or within any polymerization intiators, chain transferagents or end groups that may be present in the polymer. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that they contain, on average, less thanone ether linkage per polymer chain within the composition. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that they contain essentially no etherlinkages.

In certain embodiments where an aliphatic polycarbonate is derived frommonosubstituted epoxides (e.g. such as propylene oxide, 1,2-butyleneoxide, epichlorohydrin, epoxidized alpha olefins, or a glycidolderivative), the aliphatic polycarbonate is characterized in that it isregioregular. Regioregularity may be expressed as the percentage ofadjacent monomer units that are oriented in a head-to-tail arrangementwithin the polymer chain. In certain embodiments, aliphaticpolycarbonate chains in the inventive polymer compositions have ahead-to-tail content higher than about 80%. In certain embodiments, thehead-to-tail content is higher than about 85%. In certain embodiments,the head-to-tail content is higher than about 90%. In certainembodiments, the head-to-tail content is greater than about 91%, greaterthan about 92%, greater than about 93%, greater than about 94%, orgreater than about 95%. In certain embodiments, the head-to-tail contentof the polymer is as determined by proton or carbon-13 NMR spectroscopy.

In certain embodiments, aliphatic polycarbonate polyols useful for thepresent invention have a viscosity controlled to be within a particularrange. The preferred range may depend upon a particular application andmay be controlled to be within the normal range for a particularapplication.

In certain embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a rigid foam or a thermoplastic composition, thepolyol has a viscosity, as measured at a temperature of at least 20° C.but less than 70° C., of less than about 30,000 cps. In certainembodiments, such polyols have a viscosity less than about 20,000 cps,less than about 15,000 cps, less than about 12,000 cps, or less thanabout 10,000 cps. In certain embodiments, such polyols have a viscositybetween about 600 and about 30,000 cps. In certain embodiments, suchpolyols have a viscosity between about 2,000 and about 20,000 cps. Incertain embodiments, such polyols have a viscosity between about 5,000and about 15,000 cps.

In other embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a flexible foam, the polyol has a viscosity, asmeasured at a temperature of at least 20° C. but less than 70° C., ofless than about 10,000 cps. In certain embodiments, such polyols have aviscosity less than about 8,000 cps, less than about 6,000 cps, lessthan about 3,000 cps, or less than about 2,000 cps. In certainembodiments, such polyols have a viscosity between about 1,000 and about10,000 cps. In certain embodiments, such polyols have a viscositybetween about 1,000 and about 6,000 cps.

In certain embodiments, the polyol viscosity values described aboverepresent the viscosity as measured at 25° C. In certain embodiments,the viscosity values above represent the viscosity as measured at 30°C., 40° C., 50° C., 60° C. or 70° C.

In certain embodiments, aliphatic polycarbonate polyols useful for thepresent invention have a Tg within a particular range. The desired Tgwill vary with the application and may be controlled to be within theknown normal range for a particular application. In certain embodiments,where the polyol is used in the formulation of a flexible foamcomposition, the polyol has a Tg less than about 20° C. In certainembodiments, such polyols have Tg less than about 15° C., less thanabout 10° C., less than about 5° C., less than about 0° C., less thanabout −10° C., less than about −20° C., or less than about 40° C. Incertain embodiments, such polyols have a Tg between about −30° C. andabout −20° C. In certain embodiments, such polyols have a Tg betweenabout −30° C. and about −20° C.

In certain embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a rigid foam composition, the polyol has a Tggreater than about −30° C. In certain embodiments, such polyols have Tggreater than about −20° C., greater than about −10° C., greater thanabout 0° C., greater than about 10° C., greater than about 15° C., orgreater than about 25° C. In certain embodiments, such polyols have a Tgbetween about −10° C. and about 30° C. In certain embodiments, suchpolyols have a Tg between about 0° C. and about 20° C.

In certain embodiments, compositions of the present invention comprisealiphatic polycarbonate polyols having a structure P1:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain,independently selected from the group consisting of —H, fluorine, anoptionally substituted C₁₋₃₀ aliphatic group, and an optionallysubstituted C₁₋₂₀ heteroaliphatic group, and an optionally substitutedC₆₋₁₀ aryl group, where any two or more of R¹, R², R³, and R⁴ mayoptionally be taken together with intervening atoms to form one or moreoptionally substituted rings optionally containing one or moreheteroatoms;

Y is, at each occurrence, independently —H or the site of attachment ofa moiety containing another reactive end group such as those describedhereinabove;

n is at each occurrence, independently an integer from about 2 to about100;

is a multivalent moiety; and

x and y are each independently an integer from 0 to 6, where the sum ofx and y is between 2 and 6.

In certain embodiments, the multivalent moiety

embedded within the aliphatic polycarbonate chain is derived from apolyfunctional chain transfer agent having two or more sites from whichepoxide/CO₂ copolymerization can occur. In certain embodiments, suchcopolymerizations are performed in the presence of polyfunctional chaintransfer agents as exemplified in PCT publication WO/2010/028362.

In certain embodiments, a polyfunctional chain transfer agent has aformula:

wherein each of

, x, and y is as defined above and described in classes and subclassesherein.

In certain embodiments, aliphatic polycarbonate chains in the inventivepolymer compositions are derived from the copolymerization of one ormore epoxides with carbon dioxide in the presence of such polyfunctionalchain transfer agents as shown in Scheme 2:

In certain embodiments, aliphatic polycarbonate chains in polymercompositions of the present invention comprise chains with a structureP2:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in the classes and subclassesherein.

In certain embodiments where aliphatic polycarbonate chains have astructure P2,

is derived from a dihydric alcohol. In such instances

represents the carbon-containing backbone of the dihydric alcohol, whilethe two oxygen atoms adjacent to

are derived from the —OH groups of the diol. For example, if thepolyfunctional chain transfer agent were ethylene glycol, then

would be —CH₂CH₂— and P2 would have the following structure:

It will be apparent to the skilled artisan, that this is the case forthe other polyfunctional chain transfer agents described herein—there isa nexus between the structure of the chain transfer agent employed andthe structure of

in the resulting polyol.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises aC₂₋₄₀ diol. In certain embodiments, the dihydric alcohol is selectedfrom the group consisting of: 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,1,5-pentanediol, 2,2-dimethylpropane-1,3-diol,2-butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentane diol,2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane diol, 1,5-hexanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide,glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters,trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritoldiethers, and alkoxylated derivatives of any of these.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol is selectedfrom the group consisting of: diethylene glycol, triethylene glycol,tetraethylene glycol, higher poly(ethylene glycol), such as those havingnumber average molecular weights of from 220 to about 2000 g/mol,dipropylene glycol, tripropylene glycol, and higher poly(propyleneglycols) such as those having number average molecular weights of from234 to about 2000 g/mol.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises analkoxylated derivative of a compound selected from the group consistingof: a diacid, a diol, or a hydroxy acid. In certain embodiments, thealkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises apolymeric diol. In certain embodiments, a polymeric diol is selectedfrom the group consisting of polyethers, polyesters, hydroxy-terminatedpolyolefins, polycarbonate polyols derived from diols and phosgene (orits reactive equivalents); polyether-copolyesters, polyetherpolycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers,and alkoxylated analogs of any of these. In certain embodiments, thepolymeric diol has an average molecular weight less than about 2000g/mol.

In certain embodiments,

is derived from a polyhydric alcohol with more than two hydroxy groups.In certain embodiments, the aliphatic polycarbonate chains in polymercompositions of the present invention comprise aliphatic polycarbonatechains where the moiety

is derived from a triol. In certain embodiments, such aliphaticpolycarbonate chains have the structure P3:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments where

is derived from a triol, the triol is selected from the group consistingof: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol;hexane triols, trimethylol propane, trimethylol ethane,trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol monoesters, pentaerythritol mono ethers, and alkoxylated analogs of any ofthese. In certain embodiments, alkoxylated derivatives compriseethoxylated or propoxylated compounds.

In certain embodiments,

is derived from an alkoxylated derivative of a trifunctional carboxylicacid or trifunctional hydroxy acid. In certain embodiments, alkoxylatedderivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, where

is derived from a polymeric triol, the polymeric triol is selected fromthe group consisting of polyethers, polyesters, hydroxy-terminatedpolyolefins, polyether-copolyesters, polyether polycarbonates,polyoxymethylene polymers, polycarbonate-copolyesters, and alkoxylatedanalogs of any of these. In certain embodiments, the alkoxylatedpolymeric triols comprise ethoxylated or propoxylated compounds.

In certain embodiments,

is derived from a polyhydric alcohol with four hydroxy groups. Incertain embodiments, aliphatic polycarbonate chains in polymercompositions of the present invention comprise aliphatic polycarbonatechains where the moiety

is derived from a tetraol. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P4:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments,

is derived from a polyhydric alcohol with more than four hydroxy groups.In certain embodiments,

is derived from a polyhydric alcohol with six hydroxy groups. In certainembodiments, a polyhydric alcohol is dipentaerithrotol or an alkoxylatedanalog thereof. In certain embodiments, a polyhydric alcohol is sorbitolor an alkoxylated analog thereof. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P5:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments, aliphatic polycarbonates of the presentinvention comprise a combination of bifunctional chains (e.g.polycarbonates of formula P2) in combination with higher functionalchains (e.g. one or more polycarbonates of formulae P3 to P5).

In certain embodiments,

is derived from a hydroxy acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P6:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein. In such instances,

represents the carbon-containing backbone of the hydroxy acid, while theester and carbonate linkages adjacent to

are derived from the —CO₂H group and the hydroxy group of the hydroxyacid. For example, if

were derived from 3-hydroxy propanoic acid, then

would be —CH₂CH₂— and P6 would have the following structure:

In certain embodiments,

is derived from an optionally substituted C₂₋₄₀ hydroxy acid. In certainembodiments,

is derived from a polyester. In certain embodiments, such polyestershave a molecular weight less than about 2000 g/mol.

In certain embodiments, a hydroxy acid is an alpha-hydroxy acid. Incertain embodiments, a hydroxy acid is selected from the groupconsisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic,citric acid, and mandelic acid.

In certain embodiments, a hydroxy acid is a beta-hydroxy acid. Incertain embodiments, a hydroxy acid is selected from the groupconsisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3hydroxybutryic acid, L-3-hydroxybutyric acid, DL-3-hydroxy valeric acid,D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, andderivatives of salicylic acid.

In certain embodiments, a hydroxy acid is a α-ω hydroxy acid. In certainembodiments, a hydroxy acid is selected from the group consisting of: ofoptionally substituted C₃₋₂₀ aliphatic α-ω hydroxy acids and oligomericesters.

In certain embodiments, a hydroxy acid is selected from the groupconsisting of:

In certain embodiments,

is derived from a polycarboxylic acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P7:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein, and y′ is an integer from 1 to 5 inclusive.

In embodiments where the aliphatic polycarbonate chains have a structureP7,

represents the carbon-containing backbone (or a covalent bond in thecase of oxalic acid) of a polycarboxylic acid, while ester groupsadjacent to

are derived from —CO₂H groups of the polycarboxylic acid. For example,if

were derived from succinic acid (HO₂CCH₂CH₂CO₂H), then

would be —CH₂CH₂— and P7 would have the following structure:

wherein each of R¹, R², R³, R⁴, Y, and n is as defined above anddescribed in classes and subclasses herein.

In certain embodiments,

is derived from a dicarboxylic acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P8:

In certain embodiments,

is selected from the group consisting of: phthalic acid, isophthalicacid, terephthalic acid, maleic acid, succinic acid, malonic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaicacid.

In certain embodiments,

is selected from the group consisting of:

In certain embodiments, each

in the structures herein is independently selected from the groupconsisting of:

-   wherein each R^(x) is independently an optionally substituted group    selected from the group consisting of C₂₋₂₀ aliphatic, C₂₋₂₀    heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered    aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered    heterocyclic.

In certain embodiments, each

in the structures herein is independently selected from the groupconsisting of:

-   wherein R^(x) is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise:

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n are is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, R^(x), and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y, R^(x), and n is as defined above and described    in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n are is as defined above and described in classes and    subclasses herein; and each    independently represents a single or double bond.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y,    , and n is as defined above and described in classes and subclasses    herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , R^(x), —Y and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y, R^(x), and n is as defined above and described    in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y,    , and n is as defined above and described in classes and subclasses    herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of    , —Y, and n is as defined above and described in classes and    subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   wherein each of —Y and n is as defined above and described in    classes and subclasses herein.

In certain embodiments, in polycarbonates of structures P2a, P2c, P2d,P2f, P2h, P2j, P2l, P2l-a, P2n, P2p, and P2r,

is selected from the group consisting of: ethylene glycol; diethyleneglycol, triethylene glycol, 1,3 propane diol; 1,4 butane diol, hexyleneglycol, 1,6 hexane diol, propylene glycol, dipropylene glycol,tripopylene glycol, and alkoxylated derivatives of any of these.

For polycarbonates comprising repeat units derived from two or moreepoxides, such as those represented by structures P2f through P2r,depicted above, it is to be understood that the structures drawn mayrepresent mixtures of positional isomers or regioisomers that are notexplicitly depicted. For example, the polymer repeat unit adjacent toeither end group of the polycarbonate chains can be derived from eitherone of the two epoxides comprising the copolymers, or from only one ofthe two epoxides. Thus, while the polymers may be drawn with aparticular repeat unit attached to an end group, the terminal repeatunits might be derived from either of the two epoxides and a givenpolymer composition might comprise a mixture of all of the possibilitiesin varying ratios. The ratio of these end-groups can be influenced byseveral factors including the ratio of the different epoxides used inthe polymerization, the structure of the catalyst used, the reactionconditions used (i.e temperature, CO₂ pressure, etc.) as well as by thetiming of addition of reaction components. Similarly, while the drawingsabove may show a defined regiochemistry for repeat units derived fromsubstituted epoxides, the polymer compositions will, in some cases,contain mixtures of regioisomers. The regioselectivity of a givenpolymerization can be influenced by numerous factors including thestructure of the catalyst used and the reaction conditions employed. Toclarify, this means that the composition represented by structure P2rabove, may contain a mixture of several compounds as shown in thediagram below. This diagram shows the isomers graphically for polymerP2r, where the structures below the depiction of the chain show eachregio- and positional isomer possible for the monomer unit adjacent tothe chain transfer agent and the end groups on each side of the mainpolymer chain. Each end group on the polymer may be independentlyselected from the groups shown on the left or right while the centralportion of the polymer including the chain transfer agent and its twoadjacent monomer units may be independently selected from the groupsshown. In certain embodiments, the polymer composition comprises amixture of all possible combinations of these. In other embodiments, thepolymer composition is enriched in one or more of these.

In certain embodiments, the aliphatic polycarbonate polyol is selectedfrom the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, and mixtures of anytwo or more of these.

-   wherein, t is an integer from 1 to 12 inclusive, and R¹ is    independently at each occurrence —H, or —CH₃.

In certain embodiments, the aliphatic polycarbonate polyol is selectedfrom the group consisting of:

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol, apolydispersity index less than about 1.25, at least 85% carbonatelinkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 500 g/mol, a polydispersity index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 1,000 g/mol, a polydispersity index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 2,000 g/mol, a polydispersity index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 3,000 g/mol, a polydispersity index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol, apolydispersity index less than about 1.25, at least 95% carbonatelinkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q2 having a number averagemolecular weight of about 500 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having a number averagemolecular weight of about 1,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having a number averagemolecular weight of about 2,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having a number averagemolecular weight of about 3,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having a numberaverage molecular weight of between about 500 g/mol and about 3,000g/mol, a polydispersity index less than about 1.25, at least 90%carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having a numberaverage molecular weight of about 500 g/mol, a polydispersity index lessthan about 1.25, at least 90% carbonate linkages, and at least 98% —OHend groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having a numberaverage molecular weight of about 1,000 g/mol, a polydispersity indexless than about 1.25, at least 90% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having a numberaverage molecular weight of about 2,000 g/mol (e.g. n is on averagebetween about 10 and about 11), a polydispersity index less than about1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having a numberaverage molecular weight of about 3,000 g/mol, a polydispersity indexless than about 1.25, at least 95% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene carbonate) of formula Q4 having a number average molecularweight of between about 500 g/mol and about 3,000 g/mol (e.g. each n isbetween about 4 and about 16), a polydispersity index less than about1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q4 having a number average molecularweight of about 500 g/mol, a polydispersity index less than about 1.25,at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q4 having a number average molecularweight of about 1,000 g/mol, a polydispersity index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q4 having a number average molecularweight of about 2,000 g/mol, a polydispersity index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q4 having a number average molecularweight of about 3,000 g/mol, a polydispersity index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups.

Poly(propylene carbonate) of formula Q5 having a number averagemolecular weight of between about 500 g/mol and about 3,000 g/mol, apolydispersity index less than about 1.25, at least 95% carbonatelinkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q5 having a number averagemolecular weight of about 500 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q5 having a number averagemolecular weight of about 1,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q5 having a number averagemolecular weight of about 2,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q5 having a number averagemolecular weight of about 3,000 g/mol, a polydispersity index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having a numberaverage molecular weight of between about 500 g/mol and about 3,000g/mol, a polydispersity index less than about 1.25, at least 90%carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having a numberaverage molecular weight of about 500 g/mol, a polydispersity index lessthan about 1.25, at least 90% carbonate linkages, and at least 98% —OHend groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having a numberaverage molecular weight of about 1,000 g/mol, a polydispersity indexless than about 1.25, at least 90% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having a numberaverage molecular weight of about 2,000 g/mol (e.g. n is on averagebetween about 10 and about 11), a polydispersity index less than about1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;and

Poly(ethylene-co-propylene carbonate) of formula Q6 having a numberaverage molecular weight of about 3,000 g/mol, a polydispersity indexless than about 1.25, at least 95% carbonate linkages, and at least 98%—OH end groups.

In certain embodiments, the embedded chain transfer agent

is a moiety derived from a polymeric diol or higher polyhydric alcohol.In certain embodiments, such polymeric alcohols are polyether orpolyester polyols. In certain embodiments

is a polyether polyol comprising ethylene glycol or propylene glycolrepeating units (—OCH₂CH₂O—, or —OCH₂CH(CH₃)O—) or combinations ofthese. In certain embodiments,

is a polyester polyol comprising the reaction product of a diol and adiacid, or a material derived from ring-opening polymerization oflactones.

In certain embodiments where

comprises a polyether diol, the aliphatic polycarbonate polyol has astructure Q7:

wherein,

R^(q) is at each occurrence in the polymer chain independently —H or—CH₃;

R^(a) is —H, or —CH₃;

q and q′ are independently an integer from about 2 to about 40; and

and n is as defined above and in the examples and embodiments herein.

In certain embodiments, an aliphatic polycarbonate polyol is selectedfrom the group consisting of:

-   wherein each of R^(a), R^(q), q, q′, and n is as defined above and    described in classes and subclasses herein.

In certain embodiments, where aliphatic polycarbonate polyols comprisecompounds conforming to structure Q7, the moiety

is derived from a commercially available polyether polyol such as thosetypically used in the formulation of polyurethane foam compositions.

In certain embodiments where

comprises a polyester diol, the aliphatic polycarbonate polyol has astructure Q8:

wherein,

-   -   c is at each occurrence in the polymer chain independently an        integer from 0 to 6;    -   d is at each occurrence in the polymer chain independently an        integer from 1 to 11; and    -   each of R^(q), n, q, and q′ is as defined above and described in        classes and subclasses herein.

In certain embodiments, an aliphatic polycarbonate polyol is selectedfrom the group consisting of:

-   wherein each of n and q is as defined above and described in classes    and subclasses herein.

In certain embodiments, where aliphatic polycarbonate polyols comprisecompounds conforming to structure Q8, the moiety

is derived from a commercially available polyester polyol such as thosetypically used in the formulation of polyurethane foam compositions.

APPENDIX B ISOCYANATE REAGENTS

This section describes some of the polyisocyanates and that have utilityin methods and compositions of the present invention. Compositions ofthe present invention comprise isocyanate reagents or their reactionproducts. The purpose of these isocyanate reagents is to react with thereactive end groups on the aliphatic polycarbonate polyols to formhigher molecular weight structures through chain extension and/orcross-linking.

The art of polyurethane synthesis is well advanced and a very largenumber of isocyanates and related polyurethane precursors are known inthe art and available commercially. While this section of thespecification describes isocyanates suitable for use in certainembodiments of the present invention, it is to be understood that it iswithin the capabilities of one skilled in the art of polyurethaneformulation to use alternative isocyanates along with the teachings ofthis disclosure to formulate additional compositions of matter withinthe scope of the present invention. Descriptions of suitable isocyanatecompounds and related methods can be found in: Chemistry and Technologyof Polyols for Polyurethanes Ionescu, Mihail 2005 (ISBN978-1-84735-035-0), and H. Ulrich, “Urethane Polymers,” Kirk-OthmerEncyclopedia of Chemical Technology, 1997 the entirety of each of whichis incorporated herein by reference.

In certain embodiments, the isocyanate reagents comprise two or moreisocyanate groups per molecule. In certain embodiments the isocyanatereagents are diisocyanates. In other embodiments, the isocyanatereagents are higher polyisocyanates such as triisocyanates,tetraisocyanates, isocyanate polymers or oligomers, and the like. Incertain embodiments, the isocyanate reagents are aliphaticpolyisocyanates or derivatives or oligomers of aliphaticpolyisocyanates. In other embodiments, the isocyanates are aromaticpolyisocyanates or derivatives or oligomers of aromatic polyisocyanates.In certain embodiments, the compositions may comprise mixtures of anytwo or more of the above types of isocyanates.

In certain embodiments, the isocyanate component used in the formulationof the novel materials of the present invention have a functionality of2 or more. In certain embodiments, the isocyanate component of theinventive materials comprise a mixture of diisocyanates and higherisocyanates formulated to achieve a particular functionality number fora given application. In certain embodiments, where the inventivecomposition is a flexible foam or a soft elastomer, the isocyanateemployed has a functionality of about 2. In certain embodiments, suchisocyanates have a functionality between about 2 and about 2.7. Incertain embodiments, such isocyanates have a functionality between about2 and about 2.5. In certain embodiments, such isocyanates have afunctionality between about 2 and about 2.3. In certain embodiments,such isocyanates have a functionality between about 2 and about 2.2.

In other embodiments, where the inventive composition is a rigid foam ora thermoplastic, the isocyanate employed has a functionality greaterthan 2. In certain embodiments, such isocyanates have a functionalitybetween about 2.3 and about 4. In certain embodiments, such isocyanateshave a functionality between about 2.5 and about 3.5. In certainembodiments, such isocyanates have a functionality between about 2.6 andabout 3.1. In certain embodiments, such isocyanates have a functionalityof about 3.

In certain embodiments, an isocyanate reagent is selected from the groupconsisting of: 1,6-hexamethylaminediisocyanate (HDI), isophoronediisocyanate (IPDI), 4,4′ methylene-bis(cyclohexyl isocyanate) (H₁₂MDI),2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI),diphenylmethane-4,4′-diisocyanate (MDI),diphenylmethane-2,4′-diisocyanate (MDI), xylylene diisocyanate (XDI),1,3-Bis(isocyanatomethyl)cyclohexane (H6-XDI),2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI),p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-1,8-ictanediisocyanate (TIN), triphenylmethane-4,4′,4″triisocyanate,Tris(p-isocyanatomethyl)thiosulfate, 1,3-Bis(isocyanatomethyl)benzene,1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate,1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysinediisocyanate, and mixtures of any two or more of these.

Isocyanates suitable for certain embodiments of the present inventionare available commercially under various trade names. Examples ofsuitable commercially available isocyanates include materials sold undertrade names: Desmodur® (Bayer Material Science), Tolonate® (Perstorp),Takenate® (Takeda), Vestanat® (Evonik), Desmotherm® (Bayer MaterialScience), Bayhydur® (Bayer Material Science), Mondur (Bayer MaterialScience), Suprasec (Huntsman Inc.), Lupranate® (BASF), Trixene(Baxenden), Hartben® (Benasedo), Ucopol® (Sapici), and Basonat® (BASF).Each of these trade names encompasses a variety of isocyanate materialsavailable in various grades and formulations. The selection of suitablecommercially-available isocyanate materials as reagents to producepolyurethane compositions for a particular application is within thecapability of one skilled in the art of polyurethane technology usingthe teachings and disclosure of this patent application along with theinformation provided in the product data sheets supplied by theabove-mentioned suppliers.

Additional isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Lupranate® (BASF). In certainembodiments, the isocyanates are selected from the group consisting ofthe materials shown in Table 1:

TABLE 1 Nominal Products Description % NCO Funct. Lupranate M 4,4′ MDI33.5 2 Lupranate MS 4,4′ MDI 33.5 2 Lupranate MI 2,4′ and 4,4′ MDI Blend33.5 2 Lupranate LP30 Liquid Pure 4,4′ MDI 33.1 2 Lupranate 227Monomeric/Modified MDI Blend 32.1 2 Carbodiimide Modified MDI Lupranate5143 Carbodiimide Modified 4,4′ MDI 29.2 2.2 Lupranate CarbodiimideModified 4,4′ MDI 29.5 2.2 MM103 Lupranate 219 Carbodiimide Modified4,4′ MDI 29.2 2.2 Lupranate 81 Carbodiimide Modified MDI 29.5 2.2Lupranate 218 Carbodiimide Modified MDI 29.5 2.2 Polymeric MDI (PMDI)Lupranate M10 Low Funct. Polymeric 31.7 2.2 Lupranate Polymeric MDIVariant 31.5 2.7 R2500U Lupranate M20S Mid-Functionality Polymeric 31.52.7 Lupranate Mid-Functionality Polymeric 31.5 2.7 M20FB Lupranate M70LHigh-Functionality Polymeric 31 3 Lupranate M200 High-FunctionalityPolymeric 30 3.1 Polymeric MDI Blends and Derivatives Lupranate 241 LowFunctionality Polymeric 32.6 2.3 Lupranate 230 Low Viscosity Polymeric32.5 2.3 Lupranate 245 Low Viscosity Polymeric 32.3 2.3 Lupranate MidFunctionality Polymeric 32.3 2.4 TF2115 Lupranate 78 Mid FunctionalityPolymeric 32 2.3 Lupranate 234 Low Functionality Polymeric 32 2.4Lupranate 273 Low Viscosity Polymeric 32 2.5 Lupranate 266 Low ViscosityPolymeric 32 2.5 Lupranate 261 Low Viscosity Polymeric 32 2.5 Lupranate255 Low Viscosity Polymeric 31.9 2.5 Lupranate 268 Low ViscosityPolymeric 30.6 2.4 Select MDI Prepolymers Lupranate 5010 HigherFunctional Prepolymer 28.6 2.3 Lupranate 223 Low Visc. Derivative ofPure MDI 27.5 2.2 Lupranate 5040 Mid Functional, Low Viscosity 26.3 2.1Lupranate 5110 Polymeric MDI Prepolymer 25.4 2.3 Lupranate 4,4′ MDIPrepolymer 23 2 MP102 Lupranate 5090 Special 4,4′ MDI Prepolymer 23 2.1Lupranate 5050 Mid Functional, Mid NCO Prepol 21.5 2.1 Lupranate 5030Special MDI Prepolymer 18.9 NA Lupranate 5080 2,4′-MDI EnhancedPrepolymer 15.9 2 Lupranate 5060 Low Funct, Higher MW Prepol 15.5 2Lupranate 279 Low Funct, Special Prepolymer 14 2 Lupranate 5070 SpecialMDI Prepolymer 13 2 Lupranate 5020 Low Functionality, Low NCO 9.5 2Toluene Diisocyanate (TDI) Lupranate T80- 80/20:2.4/2.6 TDI 48.3 2Lupranate T80- High Acidity TDI 48.3 2 Lupranate 802080/20:TDI/Polymeric MDI 44.6 2.1

Other isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Desmodur® available from BayerMaterial Science. In certain embodiments, the isocyanates are selectedfrom the group consisting of the materials shown in Table 2:

TABLE 2 Trade Name Description Desmodur ®  2460 M Monomericdiphenylmethane diisocyanate with high 2,4′-isomer content Desmodur ® 44 M A monomeric diphenylmethane-4,4′-diisocyanate (MDI). Desmodur ®  44MC Desmodur 44 MC Flakes is a monomeric diphenylmethane-4,4′-diisocyanate (MDI). Desmodur ®  BL 1100/1 Blocked aromaticpolyisocyanate based on TDI Desmodur ®  BL 1265 Blocked aromaticpolyisocyanate based on TDI MPA/X Desmodur ®  BL 3175 SN Blocked,aliphatic polyisocyanate based on HDI Desmodur ®  BL 3272 MPA Blockedaliphatic polyisocyanate based on HDI Desmodur ®  BL 3370 MPA Blockedaliphatic polyisocyanate based on HDI Desmodur ®  BL 3475 Aliphaticcrosslinking stoving urethane resin based on HDI/IPDI BA/SN Desmodur ® BL 3575/1 Blocked aliphatic polyisocyanate based on HDI MPA/SNDesmodur ®  BL 4265 SN Blocked, aliphatic polyisocyanate based on IPDIDesmodur ®  BL 5375 Blocked aliphatic polyisocyanate based on H 12 MDIDesmodur ®  CD-L Desmodur CD-L is a modified isocyanate based ondiphenylmethane- 4,4′-diisocyanate. Desmodur ®  CD-S Desmodur CD-S is amodified isocyanate based on diphenylmethane- 4,4′-diisocyanate.Desmodur ®  D XP 2725 Hydrophilically modified polyisocyanateDesmodur ®  DA-L Hydrophilic aliphatic polyisocyanate based onhexamethylene diisocyanate Desmodur ®  DN Aliphatic polyisocyanate oflow volatility Desmodur ®  E 1160 Aromatic polyisocyanate prepolymerbased on toluene diisocyanate Desmodur ®  E 1361 BA Aromaticpolyisocyanate prepolymer based on toluylene diisocyanate Desmodur ®  E1361 Aromatic polyisocyanate prepolymer based on toluene diisocyanateMPA/X Desmodur ®  E 14 Aromatic polyisocyanate prepolymer based ontoluene diisocyanate Desmodur ®  E 15 Aromatic polyisocyanate prepolymerbased on toluene diisocyanate. Desmodur ®  E 1660 Aromaticpolyisocyanate prepolymer based on toluene diisocyanate. Desmodur ®  E1750 PR Polyisocyanate prepolymer based on toluene diisocyanateDesmodur ®  E 20100 Modified polyisocyanate prepolymer based ondiphenylmethane diisocyanate. Desmodur ®  E 21 Aromatic polyisocyanateprepolymer based on diphenylmethane diisocyanate (MDI). Desmodur ®  E2190 X Aromatic polyisocyanate prepolymer based on diphenylmethanediisocyanate (MDI) Desmodur ®  E 22 Aromatic polyisocyanate prepolymerbased on diphenylmethane diisocyanate. Desmodur ®  E 2200/76 Desmodur E2200/76 is a prepolymer based on (MDI) with isomers. Desmodur ®  E 23Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate(MDI). Desmodur ®  E 29 Polyisocyanate prepolymer based ondiphenylmethane diisocyanate. Desmodur ®  E 305 Desmodur E 305 is alargely linear aliphatic NCO prepolymer based on hexamethylenediisocyanate. Desmodur ®  E 3265 Aliphatic polyisocyanate prepolymerbased on hexamethylene MPA/SN diisocyanate (HDI) Desmodur ®  E 3370Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanateDesmodur ®  E XP 2605 Polyisocyanate prepolymer based on toluenediisocyanate and diphenylmethan diisocyanate Desmodur ®  E XP 2605Polyisocyanate prepolymer based on toluene diisocyanate anddiphenylmethan diisocyanate Desmodur ®  E XP 2715 Aromaticpolyisocyanate prepolymer based on 2,4′-diphenylmethane diisocyanate(2,4′-MDI) and a hexanediol adipate Desmodur ®  E XP 2723 Aromaticpolyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).Desmodur ®  E XP 2726 Aromatic polyisocyanate prepolymer based on2,4′-diphenylmethane diisocyanate (2,4′-MDI) Desmodur ®  E XP 2727Aromatic polyisocyanate prepolymer based on diphenylmethanediisocyanate. Desmodur ®  E XP 2762 Aromatic polyisocyanate prepolymerbased on diphenylmethane diisocyanate (MDI). Desmodur ®  H Monomericaliphatic diisocyanate Desmodur ®  HL Aromatic/aliphatic polyisocyanatebased on toluylene diisocyanate/ hexamethylene diisocyanate Desmodur ® I Monomeric cycloaliphatic diisocyanate. Desmodur ®  IL 1351 Aromaticpolyisocyanate based on toluene diisocyanate Desmodur ®  IL 1451Aromatic polyisocyanate based on toluene diisocyanate Desmodur ®  IL BAAromatic polyisocyanate based on toluene diisocyanate Desmodur ®  IL EAAromatic polyisocyante resin based on toluylene diisocyanate Desmodur ® L 1470 Aromatic polyisocyanate based on toluene diisocyanate Desmodur ® L 67 BA Aromatic polyisocyanate based on tolulene diisocyanateDesmodur ®  L 67 MPA/X Aromatic polyisocyanate based on tolulenediisocyanate Desmodur ®  L 75 Aromatic polyisocyanate based on tolulenediisocyanate Desmodur ®  LD Low-functionality isocyanate based onhexamethylene diisocyanate (HDI) Desmodur ®  LS 2424 Monomericdiphenylmethane diisocyanate with high 2,4′-isomer content Desmodur ® MT Polyisocyanate prepolymer based on diphenylmethane diisocyanateDesmodur ®  N 100 Aliphatic polyisocyanate (HDI biuret) Desmodur ®  N3200 Aliphatic polyisocyanate (low-viscosity HDI biuret) Desmodur ®  N3300 Aliphatic polyisocyanate (HDI trimer) Desmodur ®  N 3368 BA/SNAliphatic polyisocyanate (HDI trimer) Desmodur ®  N 3368 SN Aliphaticpolyisocyanate (HDI trimer) Desmodur ®  N 3386 BA/SN Aliphaticpolyisocyanate (HDI trimer) Desmodur ®  N 3390 BA Aliphaticpolyisocyanate (HDI trimer) Desmodur ®  N 3390 BA/SN Aliphaticpolyisocyanate (HDI trimer) Desmodur ®  N 3400 Aliphatic polyisocyanate(HDI uretdione) Desmodur ®  N 3600 Aliphatic polyisocyanate(low-viscosity HDI trimer) Desmodur ®  N 3790 BA Aliphaticpolyisocyanate (high functional HDI trimer) Desmodur ®  N 3800 Aliphaticpolyisocyanate (flexibilizing HDI trimer) Desmodur ®  N 3900Low-viscosity, aliphatic polyisocyanate resin based on hexamethylenediisocyanate Desmodur ®  N 50 BA/MPA Aliphatic polyisocyanate (HDIbiuret) Desmodur ®  N 75 BA Aliphatic polyisocyanate (HDI biuret)Desmodur ®  N 75 MPA Aliphatic polyisocyanate (HDI biuret) Desmodur ®  N75 MPA/X Aliphatic polyisocyanate (HDI biuret) Desmodur ®  NZ 1Aliphatic polyisocyanate Desmodur ®  PC-N Desmodur PC-N is a modifieddiphenyl-methane-4,4′-diisocyanate (MDI). Desmodur ®  PF Desmodur PF isa modified diphenyl-methane-4,4′-diisocyanate (MDI). Desmodur ®  PL 340,60% Blocked aliphatic polyisocyanate based on IPDI BA/SN Desmodur ®  PL350 Blocked aliphatic polyisocyanate based on HDI Desmodur ®  RCSolution of a polyisocyanurate of toluene diisocyanate (TDI) in ethylacetate. Desmodur ®  RE Solution oftriphenylmethane-4,4′,4″-triisocyanate in ethyl acetate Desmodur ®  RFESolution of tris(p-isocyanatophenyl) thiophosphate in ethyl acetateDesmodur ®  RN Solution of a polyisocyanurate with aliphatic andaromatic NCO groups in ethyl acetate. Desmodur ®  T 100 Pure2,4′-toluene diisocyanate (TDI) Desmodur ®  T 65 N 2,4- and 2,6-toluenediisocyanate (TDI) in the ratio 67:33 Desmodur ®  T 80 2,4- and2,6-toluene diisocyanate (TDI) in the ratio 80:20 Desmodur ®  T 80 P2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80:20 with anincreased content of hydrolysable chlorine Desmodur ®  VH 20 NPolyisocyanate based on diphenylmethane diisocyanate Desmodur ®  VKDesmodur VK products re mixtures of diphenylmethane-4,4′- diisocyanate(MDI) with isomers and higher functional homologues Desmodur ®  VKP 79Desmodur VKP 79 is a modified diphenylmethane-4,4′-diisocyanate (MDI)with isomers and homologues. Desmodur ®  VKS 10 Desmodur VKS 10 is amixture of diphenylmethane-4,4′-diisocyanate (MDI) with isomers andhigher functional homologues (PMDI). Desmodur ®  VKS 20 Desmodur VKS 20is a mixture of diphenylmethane-4,4′-diisocyanate (MDI) with isomers andhigher functional homologues (PMDI). Desmodur ®  VKS 20 F Desmodur VKS20 F is a mixture of diphenylmethane-4,4′- diisocyanate (MDI) withisomers and higher functional homologues Desmodur ®  VKS 70 Desmodur VKS70 is a mixture of diphenylmethane-4,4′-diisocyanate (MDI) with isomersand homologues. Desmodur ®  VL Aromatic polyisocyanate based ondiphenylmethane diisocyanate Desmodur ®  VP LS 2078/2 Blocked aliphaticpolyisocyanate based on IPDI Desmodur ®  VP LS 2086 Aromaticpolyisocyanate prepolymer based on diphenylmethane diisocyanateDesmodur ®  VP LS 2257 Blocked aliphatic polyisocyanate based on HDIDesmodur ®  VP LS 2371 Aliphatic polyisocyanate prepolymer based onisophorone diisocyanate. Desmodur ®  VP LS 2397 Desmodur VP LS 2397 is alinear prepolymer based on polypropylene ether glycol anddiphenylmethane diisocyanate (MDI). It contains Desmodur ®  W Monomericcycloaliphatic diisocyanate Desmodur ®  W/1 Monomeric cycloaliphaticdiisocyanate Desmodur ®  XP 2404 Desmodur XP 2404 is a mixture ofmonomeric polyisocyanates Desmodur ®  XP 2406 Aliphatic polyisocyanateprepolymer based on isophorone diisocyanate Desmodur ®  XP 2489Aliphatic polyisocyanate Desmodur ®  XP 2505 Desmodur XP 2505 is aprepolymer containing ether groups based ondiphenylmethane-4,4′-diisocyanates (MDI) with isomers and higherDesmodur ®  XP 2551 Aromatic polyisocyanate based on diphenylmethanediisocyanate Desmodur ®  XP 2565 Low-viscosity, aliphatic polyisocyanateresin based on isophorone diisocyanate. Desmodur ®  XP 2580 Aliphaticpolyisocyanate based on hexamethylene diisocyanate Desmodur ®  XP 2599Aliphatic prepolymer containing ether groups and based onhexamethylene-1,6-diisocyanate (HDI) Desmodur ®  XP 2617 Desmodur XP2617 is a largely linear NCO prepolymer based on hexamethylenediisocyanate. Desmodur ®  XP 2665 Aromatic polyisocyanate prepolymerbased on diphenylmethane diisocyanate (MDI). Desmodur ®  XP 2675Aliphatic polyisocyanate (highly functional HDI trimer) Desmodur ®  XP2679 Aliphatic polyisocyanate (HDI allophanate trimer) Desmodur ®  XP2714 Silane-functional aliphatic polyisocyanate based on hexamethylenediisocyanate Desmodur ®  XP 2730 Low-viscosity, aliphatic polyisocyanate(HDI uretdione) Desmodur ®  XP 2731 Aliphatic polyisocyanate (HDIallophanate trimer) Desmodur ®  XP 2742 Modified aliphaticPolyisocyanate (HDI-Trimer), contains SiO2- nanoparticles

Additional isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Tolonate (Perstorp). In certainembodiments, the isocyanates are selected from the group consisting ofthe materials shown in Table 3:

TABLE 3 Tolonate ™  D2 a blocked aliphatic polyisocyanate, supplied at75% solids in aromatic solvent Tolonate ™  HDB a viscous solvent-freealiphatic polyisocyanate Tolonate ™  HDB-LV a solvent free low viscosityaliphatic polyisocyanate Tolonate ™  HDB 75 B an aliphaticpolyisocyanate, supplied at 75% solids in methoxy propyl acetateTolonate ™  HDB 75 BX an aliphatic polyisocyanate, supplied at 75%solids Tolonate ™  HDT a medium viscosity, solvent-free aliphaticpolyisocyanate Tolonate ™  HDT-LV is a solvent free low viscosityaliphatic polyisocyanate Tolonate ™  HDT-LV2 a solvent free, very lowviscosity aliphatic polyisocyanate Tolonate ™  HDT 90 an aliphaticpolyisocyanate, based on HDI-trimer (isocyanurate), supplied at 90%solids Tolonate ™  HDT 90 B an aliphatic polyisocyanate, based onHDI-trimer (isocyanurate), supplied at 90% solids Tolonate ™  IDT 70 Ban aliphatic polyisocyanate, based on HDI-trimer (isocyanurate),supplied at 70% solids Tolonate ™  IDT 70 S an aliphatic polyisocyanate,based on HDI-trimer (isocyanurate), supplied at 70% solids Tolonate ™  XFD 90 B a high functionality, fast drying aliphatic polyisocyanate basedon HDI- trimer, supplied at 90% solids

Other isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Mondur® available from BayerMaterial Science. In certain embodiments, the isocyanates are selectedfrom the group consisting of the materials shown in Table 4:

TABLE 4 Trade Name Description MONDUR 445 TDI/MDI blend polyisocyanate;blend of toluene diisocyanate and polymeric diphenylmethanediisocyanate; NCO weight 44.5-45.2% MONDUR 448 modified polymericdiphenylmethane diisocyanate (pMDI) prepolymer; NCO weight 27.7%;viscosity 140 mPa · s @ 25° C.; equivalent weight 152; functionality 2.2MONDUR 489 modified polymeric diphenylmethane diisocyanate (pMDI); NCOweight 31.5%; viscosity 700 mPa · s @ 25° C.; equivalent weight 133;functionality 3.0 MONDUR 501 modified monomeric diphenylmethanediisocyanate (mMDI); isocyanate- terminated polyester prepolymer; NCOweight 19.0%; viscosity 1,100 mPa · s @ 25° C.; equivalent weight 221;functionality 2 MONDUR 541 polymeric diphenylmethane diisocyanate(pMDI); binder for composite wood products and as a raw material inadhesive formulations; NCO weight 31.5%; viscosity 200 mPa · s @ 25° C.MONDUR 582 polymeric diphenylmethane diisocyanate (pMDI); binder forcomposite wood products and as a raw material in adhesive formulations;NCO weight 31.0%; viscosity 200 mPa · s @ 25° C. MONDUR 541-Lightpolymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.0%;viscosity 70 mPa · s @ 25° C.; equivalent weight 131; functionality 2.5MONDUR 841 modified polymeric MDI prepolymer; NCO, Wt 30.5%; Acidity, Wt0.02%; Amine Equivalent 132; Viscosity at 25° C., mPa · s 350; Specificgravity at 25° C. 1.24; Flash Point, PMCC, ° F. > 200 MONDUR 1437modified diphenylmethane diisocyanate (mMDI); isocyanate-terminatedpolyether prepolymer; NCO weight 10.0%; viscosity 2,500 mPa · s @ 25°C.; equivalent weight 420; functionality 2 MONDUR 1453 modifieddiphenylmethane diisocyanate (mMDI); isocyanate-terminated polyetherprepolymer based on polypropylene ether glycol (PPG); NCO weight 16.5%;viscosity 600 mPa · s @ 25° C.; equivalent weight 254; functionality 2MONDUR 1515 modified polymeric diphenylmethane diisocyanate (pMDI)prepolymer; used in the production of rigid polyurethane foams,especially for the appliance industry; NCO weight 30.5%; viscosity 350mPa · s @ 25° C. MONDUR 1522 modified monomeric 4,4-diphenylmethanediisocyanate (mMDI); NCO weight 29.5%; viscosity 50 mPa · s @ 25° C.;equivalent weight 143; functionality 2.2 MONDUR MA-2300 modifiedmonomeric MDI, allophanate-modified 4,4′-diphenylmethane diisocyanate(mMDI); NCO weight 23.0%; viscosity 450 mPa · s @ 25° C.; equivalentweight 183; functionality 2.0 MONDUR MA 2600 modified monomeric MDI,allophanate-modified 4,4′-diphenylmethane diisocyanate (mMDI); NCOweight 26.0%; viscosity 100 mPa · s @ 25° C.; equivalent weight 162;functionality 2.0 MONDUR MA 2601 aromatic diisocyanate blend,allophanate-modified 4,4′-diphenylmethane diisocyanate (MDI) blendedwith polymeric diphenylmethane diisocyanate (pMDI) containing2,4′-isomer; NCO weight 29.0%; viscosity 60 mPa · s @ 25° C.; equivalentweight 145; functionality 2.2 MONDUR MA 2603 MDI prepolymer;isocyanate-terminated (MDI) prepolymer blended with anallophanate-modified 4,4′-diphenylmethane diisocyanate (MDI); NCO weight16.0%; viscosity 1,050 mPa · s @ 25° C.; equivalent weight 263;functionality 2.0 MONDUR MA-2902 modified monomeric MDI,allophanate-modified 4,4′-diphenylmethane dusocyanate (mMDI); NCO weight29.0%; viscosity 40 mPa · s @ 25° C.; equivalent weight 145;functionality 2.0 MONDUR MA-2903 modified monomeric MDI;isocyanate-terminated (MDI) prepolymer; NCO weight 19.0%; viscosity 400mPa · s @ 25° C.; equivalent weight 221; functionality 2.0 MONDURMA-2904 Allophanate-modified MDI polyether prepolymer; NCO weight 12.0%;viscosity 1,800 mPa · s @ 25° C.; equivalent weight 350; functionalityof 2.0 MONDUR MB high-purity grade difunctional isocyanante,diphenylmethane 4,4′-diiscocyanate; used in production of polyurethaneelastomers, adhesives, coatings and intermediate polyurethane products;appearance colorless solid or liquid; specific gravity @ 50° C. ± 15.51.19; flash point 202° C. PMCC; viscosity (in molten form) 4.1 mPa · S;bult density 10 lb/gal (fused) or 9.93 lb/gal (molten); freezingtemperature 39° C. MONDUR MLQ monomeric diphenylmethan diisocyanate;used in a foams, cast elastomers, coatings and andesives; appearancelight yellow clear liquid, NCO 33.4% wt; 1.19 specific gravity at 25°C., 196° C. flash point, DIN 51758; 11-15° C. freezing temperatureMONDUR MQ high-purity-grade difunctional isocyanate, diphenylmethane4,4′-diisocyanate (MDI); used in production of solid polyurethaneelastomers, adhesives, coatings and in intermediate polyurethaneproducts; appearance colorless solid or liquid; specific gravity 1.19 @50° C.; flash point 202° C. PMCC; viscosity 4.1 mPa · S; bulk density 10lb./gal (fused) or 9.93 lb./gal (molten); freezing temperature 39° C.MONDUR MR polymeric diphenylmethane diisocyanate (pMDI); NCO weight31.5%; viscosity 200 mPa · s @ 25° C.; equivalent weight 133;functionality 2.8 MONDUR MR polymeric diphenylmethane diisocyanate(pMDI); NCO weight 31.5%; viscosity LIGHT 200 mPa · s @ 25° C.;equivalent weight 133; functionality 2.8 MONDUR MR-5 polymericdiphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 50 mPa· s @ 25° C.; equivalent weight 129; functionality 2.4 MONDUR MRS 2,4rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%;viscosity 200 mPa · s @ 25° C.; equivalent weight 133; functionality 2.6MONDUR MRS 2 2,4′ rich polymeric diphenylmethane diisocyanate (pMDI);NCO weight 33.0%; viscosity 25 mPa · s @ 25° C.; equivalent weight 127;functionality 2.2 MONDUR MRS-4 2,4′ rich polymeric diphenylmethanediisocyanate (pMDI); NCO weight 32.5%; viscosity 40 mPa · s @ 25° C.;equivalent weight 129; functionality 2.4 MONDUR MRS-5 2,4′ richpolymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.3%;viscosity 55 mPa · s @ 25° C.; equivalent weight 130; functionality 2.4MONDUR PC modified 4,4′ diphenylmethane diisocyanate (mMDI); NCO weight25.8%; viscosity 145 mPa · s @ 25° C.; equivalent weight 163;functionality 2.1 MONDUR PF modified 4,4′ diphenylmethane diisocyanate(mMDI) prepolymer; NCO weight 22.9%; viscosity 650 mPa · s @ 25° C.;equivalent weight 183; functionality 2 MONDUR TD-65 monomeric toluenediisocyanate (TDI); 65/35 mixture of 2,4 and 2,6 TDI; NCO weight 48%;viscosity 3 mPa · s @ 25° C.; equivalent weight 87.5; functionality 2MONDUR TD-80 monomeric toluene diisocyanate (TDI); 80/20 mixture of the2,4 and 2,6 isomer; GRADE A NCO weight 48%; viscosity 5 mPa · s @ 25°C.; equivalent weight 87.5; functionality 2 MONDUR TD-80 monomerictoluene diisocyanate (TDI); 80/20 mixture of the 2,4 and 2,6 isomer;GRADE A/GRADE B NCO weight 48%; viscosity 5 mPa · s @ 25° C.; equivalentweight 87.5; functionality 2

APPENDIX C ADDITIVES

As described above, in some embodiments, methods and compositions of thepresent invention comprise so-called B-side mixtures comprising one ormore of the aliphatic polycarbonate polyols. To produce a foam, theB-side mixture is reacted with an A-side mixture containing one or morepolyisocyanates (or polyisocyanate precursors). Typically, one or bothof the A-side and B-side mixtures will contain additional components andadditives of various sorts. In certain embodiments, the B-side mixturesfrom which any of the foams of the present invention are producedcontain one or more additional polyols and/or one or more additives. Incertain embodiments, the additives are selected from the groupconsisting of: solvents, water, catalysts, surfactants, blowing agents,colorants, UV stabilizers, flame retardants, antimicrobials,plasticizers, cell-openers, antistatic compositions, compatibilizers,and the like. In certain embodiments, the B-side mixtures compriseadditional reactive small molecules such as amines, water, alcohols,thiols or carboxylic acids that participate in bond-forming reactionswith isocyanates.

A. Additional Polyols

In certain embodiments, the B-side mixtures of the present inventioncomprise aliphatic polycarbonate polyols as described above incombination with one or more additional polyols such as aretraditionally used in polyurethane foam compositions. In embodimentswhere additional polyols are present, they may comprise up to about 95weight percent of the total polyol content with the balance of thepolyol mixture made up of one or more aliphatic polycarbonate polyolsdescribed in Section I above and in the examples and specificembodiments herein.

In embodiments where B-side mixtures of the present invention compriseor derived from a mixture of one or more aliphatic polycarbonate polyolsand one or more additional polyols, the additional polyols are selectedfrom the group consisting of polyether polyols, polyester polyols,polystyrene polyols, polyether-carbonate polyols, polyether-estercarbonates, and mixtures of any two or more of these. In certainembodiments, B-side mixtures of the present invention comprise orderived from a mixture of one or more aliphatic polycarbonate polyols asdescribed herein and one or more other polyols selected from the groupconsisting of materials available commercially under the trade names:Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow), Caradol® (Shell),Hyperliter®, Acclaim® (Bayer Material Science), Ultracel® (BayerMaterial Science), Desmophen® (Bayer Material Science), and Arcol®(Bayer Material Science).

In certain embodiments, B-side mixtures of the present inventioncomprise mixtures containing polyether polyols in combination with oneor more aliphatic polycarbonate polyols as described herein. In certainembodiments, such polyether polyols are characterized in that they havean Mn between about 500 and about 10,000 g/mol. In certain embodiments,such polyether polyols have an Mn between about 500 and about 5,000g/mol. In certain embodiments, the polyether polyols comprisepolyethylene glycol. In certain embodiments, the polyether polyolscomprise polypropylene glycol.

Polyether polyols that may be present include those which can beobtained by known methods, for example, polyether polyols can beproduced by anionic polymerization with alkali hydroxides such as sodiumhydroxide or potassium hydroxide or alkali alcoholates, such as sodiummethylate, sodium ethylate, potassium ethylate or potassium isopropylateas catalysts and with the addition of at least one initiator moleculecontaining 2 to 8, preferably 3 to 8, reactive hydrogens or by cationicpolymerization with Lewis acids such as antimony pentachloride, borontrifluoride etherate, etc., or bleaching earth as catalysts from one ormore alkylene oxides with 2 to 4 carbons in the alkylene radical. Anysuitable alkylene oxide may be used such as 1,3-propylene oxide, 1,2-and 2,3 butylene oxide, amylene oxides, styrene oxide, and preferablyethylene oxide and propylene oxide and mixtures of these oxides. Thepolyalkylene polyether polyols may be prepared from other startingmaterials such as tetrahydrofuran and alkylene oxide-tetrahydrofuranmixtures; epihalohydrins such as epichlorohydrin; as well as aralkyleneoxides such as styrene oxide. The polyalkylene polyether polyols mayhave either primary or secondary hydroxyl groups, preferably secondaryhydroxyl groups from the addition of propylene oxide onto an initiatorbecause these groups are slower to react. Included among the polyetherpolyols are polyoxyethylene glycol, polyoxypropylene glycol,polyoxybutylene glycol, polytetramethylene glycol, block copolymers, forexample, combinations of polyoxypropylene and polyoxyethylene glycols,poly-1,2-oxybutylene and polyoxyethylene glycols,poly-1,4-tetramefhylene and polyoxyethylene glycols, and copolymerglycols prepared from blends or sequential addition of two or morealkylene oxides. The polyalkylene polyether polyols may be prepared byany known process such as, for example, the process disclosed by Wurtzin Encyclopedia of Chemical Technology, Vol. 7, pp. 257-262, publishedby Interscience Publishers, Inc. (1951) or in U.S. Pat. No. 1,922,459.Polyethers include the alkylene oxide addition products of polyhydricalcohols such as ethylene glycol, propylene glycol, dipropylene glycol,trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6hexanediol,1,7-heptanediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1-trimethylol-propane, 1,1,1trimethylolethane, pentaerythritol,1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbitol. Alsoincluded within the term “polyhydric alcohol” are compounds derived fromphenol such as 2,2-bis(4-hydroxyphenyl)-propane, commonly known asBisphenol A. Particularly preferred in the polyol composition is atleast one polyol which is initiated with a compound having at least twoprimary or secondary amine groups, a polyhydric alcohol having 4 or morehydroxyl groups, such as sucrose, or a mixture of initiators employing apolyhydric alcohol having at least 4 hydroxyl groups and compoundshaving at least two primary or secondary amine groups. Suitable organicamine initiators which may be condensed with alkylene oxides includearomatic amines-such as aniline, N-alkylphenylene-diamines, 2,4′-,2,2′-, and 4,4′-methylenedianiline, 2,6- or 2,4-toluenediamine, vicinaltoluenediamines, o-chloroaniline, p-aminoaniline,1,5-diaminonaphthalene, methylene dianiline, the various condensationproducts of aniline and formaldehyde, and the isomeric diaminotoluenes;and aliphatic amines such as mono-, di-, and trialkanolamines, ethylenediamine, propylene diamine, diethylenetriamine, methylamine,triisopropanolamine, 1,3-diaminopropane, 1,3-diaminobutane, and1,4-diaminobutane. Preferable amines include monoethanolamine, vicinaltoluenediamines, ethylenediamines, and propylenediamine. Yet anotherclass of aromatic polyether polyols contemplated for use in thisinvention are the Mannich-based polyol an alkylene oxide adduct ofphenol/formaldehyde/alkanolamine resin, frequently called a “Mannich”polyol such as disclosed in U.S. Pat. Nos. 4,883,826; 4,939,182; and5,120, 815.

In certain embodiments where additional polyols are present, theycomprise from about 5 weight percent to about 95 weight percent of thetotal polyol content with the balance of the polyol mixture made up ofone or more aliphatic polycarbonate polyols described in Section I aboveand in the examples and specific embodiments herein. In certainembodiments, up to about 75 weight percent of the total polyol contentof the B-side mixture is aliphatic polycarbonate polyol. In certainembodiments, up to about 50 weight percent of the total polyol contentof the B-side mixture is aliphatic polycarbonate polyol. In certainembodiments, up to about 40 weight percent, up to about 30 weightpercent, up to about 25 weight percent, up to about 20 weight percent,up to about 15 weight percent, or up to about 10 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 5 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 10 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 15 weight percent, atleast about 20 weight percent, at least about 25 weight percent, atleast about 40 weight percent, or at least about 50 weight percent, ofthe total polyol content of the B-side mixture is aliphaticpolycarbonate polyol.

B. Catalysts

In certain embodiments, B-side mixtures contain one or more catalystsfor the reaction of the polyol (and water, if present) with thepolyisocyanate. Any suitable urethane catalyst may be used, includingtertiary amine compounds and organometallic compounds. Exemplarytertiary amine compounds include triethylenediamine, N-methylmorpholine,N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine,tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine,N-cocomorpholine, N,N-dimethyl-N′,N′-dimethyl isopropylpropylenediamine,N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine,1,8-Diazabicycloundec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO)triazabicyclodecene (TBD), and N-methyltriazabicyclodecene. (MTBD)Exemplary organometallic catalysts include organomercury, organolead,organoferric and organotin catalysts, with organotin catalysts beingpreferred among these. Suitable tin catalysts include stannous chloride,tin salts of carboxylic acids such as dibutyltin dilaurate, as well asother organometallic compounds such as are disclosed in U.S. Pat. No.2,846,408 and elsewhere. A catalyst for the trimerization ofpolyisocyanates, resulting in a polyisocyanurate, such as an alkalimetal alkoxide may also optionally be employed herein. Such catalystsare used in an amount which measurably increases the rate ofpolyurethane or polyisocyanurate formation.

In certain embodiments, where B-side mixtures of the present inventioncomprise catalysts, the catalysts comprise tin based materials. Incertain embodiments, tin catalysts included in the B-side mixtures areselected from the group consisting of: di-butyl tin dilaurate,dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate)and dibutyltinbis(isooctylmaleate), tin octanoate and mixtures of anytwo or more of these.

In certain embodiments, catalysts included in the B-side mixturescomprise tertiary amines. In certain embodiments, catalysts included inthe B-side mixtures are selected from the group consisting of: DABCO,pentametyldipropylenetriamine, bis(dimethylamino ethyl ether),pentamethyldiethylenetriamine, DBU phenol salt, dimethylcyclohexylamine,2,4,6-tris(N,N-dimethylaminomethyl)phenol (DMT-30),1,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine, ammonium saltsand combinations or formulations of any of these.

Typical amounts of catalyst are 0.001 to 10 parts of catalyst per 100parts by weight of total polyol in the B-side mixture. In certainembodiments, catalyst levels in the formulation, when used, rangebetween about 0.001 pph (weight parts per hundred) and about 3 pph basedon the amount of polyol present in the B-side mixture. In certainembodiments, catalyst levels range between about 0.05 pph and about 1pph, or between about 0.1 pph and about 0.5 pph.

C. Blowing Agents

In certain embodiments, B-side mixtures of the present invention containblowing agents. Blowing agents may be chemical blowing agents (typicallymolecules that react with A-side components to liberate CO₂ or othervolatile compounds) or they may be physical blowing agents (typicallymolecules with a low boiling point that vaporize during the foamformation. Many blowing agents are known in the art and may be appliedto B-side compositions of the present invention according toconventional methodology. The choice of blowing agent and the amountsadded can be a matter of routine experimentation.

In certain embodiments, the blowing agent comprises a chemical blowingagent. In certain embodiments, water is present as a blowing agent.Water functions as a blowing agent by reacting with a portion of theisocyanate in the A-side mixture to produce carbon dioxide gas.Similarly, formic acid can be included as a blowing agent. Formic acidfunctions as a blowing agent by reacting with a portion of theisocyanate to produce carbon dioxide and carbon monoxide gas.

In certain embodiments, water is present in an amount of from 0.5 to 20parts per 100 parts by weight of the polyol in the B-side composition.In certain embodiments, water is present from about 1 to 10 parts, fromabout 2 to 8 parts, or from about 4 to 6 parts per 100 parts by weightof polyol in the B-side composition. In certain embodiments, it isadvantageous not to exceed 2 parts of water, not-to exceed 1.5 parts ofwater, or not to exceed 0.75 parts of water. In certain embodiments, itis advantageous to have water absent.

In certain embodiments, formic acid is present in an amount of from 0.5to 20 parts per 100 parts by weight of the polyol in the B-sidecomposition. In certain embodiments, formic acid is present from about 1to 10 parts, from about 2 to 8 parts, or from about 4 to 6 parts per 100parts by weight of polyol in the B-side composition.

In certain embodiments physical blowing agents can be used. Suitablephysical blowing agents include hydrocarbons, fluorine-containingorganic molecules hydrocarbons, chlorocarbons, acetone, methyl formateand carbon dioxide. In some embodiments, fluorine-containing organicmolecules comprise perfluorinated compounds, chlorofluorocarbons,hydrochlorofluorocarbons, and hydrofluorocarbons. Suitablehydrofluoroalkanes are C₁₋₄ compounds including difiuoromethane (R-32),1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (R-152a),difiuorochloroethane (R-142b), trifiuoromethane (R-23),heptafluoropropane (R-227a), hexafluoropropane (R136),1,1,1-trifluoroefhane (R-133), fluoroethane (R-161),1,1,1,2,2-pentafluoropropane (R-245fa), pentafluoropropylene (R2125a),1,1,1,3-tetrafiuoropropane, tetrafhioropropylene (R-2134a),1,1,2,3,3-pentafluoropropane and 1,1,1,3,3-pentafiuoro-n-butane.

In certain embodiments, when a hydrofluorocarbon blowing agent ispresent in the B-side mixture, it is selected from the group consistingof: tetrafluoroethane (R-134a), pentafluoropropane (R-245fa) andpentafluorobutane (R-365).

Suitable hydrocarbons for use as blowing agent include nonhalogenatedhydrocarbons such as butane, isobutane, 2,3-dimethylbutane, n- andi-pentane isomers, hexane isomers, heptane isomers and cycloalkanesincluding cyclopentane, cyclohexane and cycloheptane. Preferredhydrocarbons for use as blowing agents include cyclopentane and notablyn-pentane an iso-pentane. In a certain embodiments the B-sidecomposition comprises a physical blowing agent selected from the groupconsisting of tetrafluoroethane (R-134a), pentafluoropropane (R-245fa),pentafluorobutane (R-365), cyclopentane, n-pentane and iso-pentane.

In certain embodiments where a physical blowing agent is present, it isused in an amount of from about 1 to about 20 parts per 100 parts byweight of the polyol in the B-side composition. In certain embodiments,the physical blowing agent is present from 2 to 15 parts, or from 4 to10 parts per 100 parts by weight of the polyol in the B-sidecomposition.

D. Reactive Small Molecules

In certain embodiments, B-side mixtures of the present invention includeone or more small molecules reactive toward isocyanates. In certainembodiments, reactive small molecules included in the inventive B-sidemixtures comprise organic molecules having one or more functional groupsselected from the group consisting of alcohols, amines, carboxylicacids, thiols, and combinations of any two or more of these. In someembodiments, a non-polymeric small molecule has a molecular weight lessthan 1,000 g/mol, or less than 1,500 g/mol.

In certain embodiments, B-side mixtures of the present invention includeone or more alcohols. In certain embodiments, the B-side mixturesinclude polyhydric alcohols.

In certain embodiments, reactive small molecules included in theinventive B-side mixtures comprise dihydric alcohols. In certainembodiments, the dihydric alcohol comprises a C₂₋₄₀ diol. In certainembodiments, the dihydric alcohol is selected from the group consistingof: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol,2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol,1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerolmonoethers, trimethylolpropane monoesters, trimethylolpropanemonoethers, pentaerythritol diesters, pentaerythritol diethers, andalkoxylated derivatives of any of these.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises a dihydric alcohol selected from thegroup consisting of: diethylene glycol, triethylene glycol,tetraethylene glycol, higher poly(ethylene glycol), such as those havingnumber average molecular weights of from 220 to about 2000 g/mol,dipropylene glycol, tripropylene glycol, and higher poly(propyleneglycols) such as those having number average molecular weights of from234 to about 2000 g/mol.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises an alkoxylated derivative of acompound selected from the group consisting of: a diacid, a diol, or ahydroxy acid. In certain embodiments, the alkoxylated derivativescomprise ethoxylated or propoxylated compounds.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises a polymeric diol. In certainembodiments, a polymeric diol is selected from the group consisting ofpolyethers, polyesters, hydroxy-terminated polyolefins,polyether-copolyesters, polyether polycarbonates,polycarbonate-copolyesters, and alkoxylated analogs of any of these. Incertain embodiments, the polymeric diol has an average molecular weightless than about 2000 g/mol.

In some embodiments, a reactive small molecule included in the inventiveB-side mixtures comprises a triol or higher polyhydric alcohol. Incertain embodiments, a reactive small molecule is selected from thegroup consisting of: glycerol, 1,2,4-butanetriol,2-(hydroxymethyl)-1,3-propanediol; hexane triols, trimethylol propane,trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol,pentaerythritol mono esters, pentaerythritol mono ethers, andalkoxylated analogs of any of these. In certain embodiments, alkoxylatedderivatives comprise ethoxylated or propoxylated compounds.

In some embodiments, a reactive small molecule comprises a polyhydricalcohol with four to six hydroxy groups. In certain embodiments, acoreactant comprises dipentaerithrotol or an alkoxylated analog thereof.In certain embodiments, coreactant comprises sorbitol or an alkoxylatedanalog thereof.

In certain embodiments, a reactive small molecule comprises ahydroxy-carboxylic acid having the general formula (HO)_(x)Q(COOH)_(y),wherein Q is a straight or branched hydrocarbon radical containing 1 to12 carbon atoms, and x and y are each integers from 1 to 3. In certainembodiments, a coreactant comprises a diol carboxylic acid. In certainembodiments, a coreactant comprises a bis(hydroxylalkyl) alkanoic acid.In certain embodiments, a coreactant comprises a bis(hydroxylmethyl)alkanoic acid. In certain embodiments the diol carboxylic acid isselected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoicacid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoicacid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaricacid), and 4,4′-bis(hydroxyphenyl) valeric acid. In certain embodiments,a coreactant comprises an N,N-bis(2-hydroxyalkyl)carboxylic acid.

In certain embodiments, a reactive small molecule comprises a polyhydricalcohol comprising one or more amino groups. In certain embodiments, areactive small molecule comprises an amino diol. In certain embodiments,a reactive small molecule comprises a diol containing a tertiary aminogroup. In certain embodiments, an amino diol is selected from the groupconsisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA),N-ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA),N,N-bis(hydroxyethyl)-α-amino pyridine, dipropanolamine,diisopropanolamine (DIPA), N-methyldiisopropanolamine,Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3-chloroaniline,3-diethylaminopropane-1,2-diol, 3-dimethylaminopropane-1,2-diol andN-hydroxyethylpiperidine. In certain embodiments, a coreactant comprisesa diol containing a quaternary amino group. In certain embodiments, acoreactant comprising a quaternary amino group is an acid salt orquaternized derivative of any of the amino alcohols described above.

In certain embodiments, a reactive small molecule is selected from thegroup consisting of: inorganic or organic polyamines having an averageof about 2 or more primary and/or secondary amine groups, polyalcohols,ureas, and combinations of any two or more of these. In certainembodiments, a reactive small molecule is selected from the groupconsisting of: diethylene triamine (DETA), ethylene diamine (EDA),meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methylpentane diamine, and the like, and mixtures thereof. Also suitable forpractice in the present invention are propylene diamine, butylenediamine, hexamethylene diamine, cyclohexylene diamine, phenylenediamine, tolylene diamine, 3,3-dichlorobenzidene,4,4′-methylene-bis-(2-chloroaniline), 3,3-dichloro-4,4-diaminodiphenylmethane, and sulfonated primary and/or secondary amines. Incertain embodiments, reactive small molecule is selected from the groupconsisting of: hydrazine, substituted hydrazines, hydrazine reactionproducts, and the like, and mixtures thereof. In certain embodiments, areactive small molecule is a polyalcohol including those having from 2to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such asethylene glycol, diethylene glycol, neopentyl glycol, butanediols,hexanediol, and the like, and mixtures thereof. Suitable ureas includeurea and its derivatives, and the like, and mixtures thereof.

In certain embodiments, reactive small molecules containing at least onebasic nitrogen atom are selected from the group consisting of: mono-,bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic orheterocyclic primary amines, N-methyl diethanolamine, N-ethyldiethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine,N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyldiethanolamine, N-stearyl diethanolamine, ethoxylated coconut oil fattyamine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyldiisopropanolamine, N-propyl diisopropanolamine, N-butyldiisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline,N,N-diethoxyl toluidine, N,N-diethoxyl-1-aminopyridine, N,N′-diethoxylpiperazine, dimethyl-bis-ethoxyl hydrazine,N,N′-bis-(2-hydroxyethyl)-N,N′-diethylhexahydr op-phenylenediamine,N-12-hydroxyethyl piperazine, polyalkoxylated amines, propoxylatedmethyl diethanolamine, N-methyl-N,N-bis-3-aminopropylamine,N-(3-aminopropyl)-N,N′-dimethyl ethylenediamine,N-(3-aminopropyl)-N-methyl ethanolamine,N,N′-bis-(3-aminopropyl)-N,N′-dimethyl ethylenediamine,N,N′-bis-(3-aminopropyl)-piperazine, N-(2-aminoethyl)-piperazine, N,N′-bisoxyethyl propylenediamine, 2,6-diaminopyridine,diethanolaminoacetamide, diethanolamidopropionamide,N,N-bisoxyethylphenyl thiosemicarbazide, N,N-bis-oxyethylmethylsemicarbazide, p,p′-bis-aminomethyl dibenzyl methylamine,2,6-diaminopyridine, 2-dimethylaminomethyl-2-methylpropanel, 3-diol. Incertain embodiments, chain-extending agents are compounds that containtwo amino groups. In certain embodiments, chain-extending agents areselected from the group consisting of: ethylene diamine,1,6-hexamethylene diamine, and 1,5-diamino-1-methyl-pentane.

E. Additives

In addition to the above components, A-side or B-side mixtures of thepresent invention may optionally contain various additives as are knownin the art of polyurethane foam technology. Such additives may include,but are not limited to compatibilizers, colorants, surfactants, flameretardants, antistatic compounds, antimicrobials, UV stabilizers,plasticizers, and cell openers.

Colorants

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable colorants. Many foam products are colorcoded during manufacture to identify product grade, to concealyellowing, or to make a consumer product. The historical method ofcoloring foam was to blend in traditional pigments or dyes. Typicalinorganic coloring agents included titanium dioxide, iron oxides andchromium oxide. Organic pigments originated from the azo/diazo dyes,phthalocyanines and dioxazines, as well as carbon black. Typicalproblems encountered with these colorants included high viscosity,abrasive tendencies, foam instability, foam scorch, migrating color anda limited range of available colors. Recent advances in the developmentof polyol-bound colorants are described in:

-   Miley, J. W.; Moore, P. D. “Reactive Polymeric Colorants For    Polyurethane”, Proceedings Of The SPI-26th Annual Technical    Conference; Technomic: Lancaster, Pa., 1981; 83-86.-   Moore, P. D.; Miley, J. W.; Bates, S. H.; “New Uses For Highly    Miscible Liquid Polymeric Colorants In The Manufacture of Colored    Urethane Systems”; Proceedings of the SPI-27th Annual    Technical/Marketing Conference; Technomic: Lancaster, Pa., 1982;    255-261.-   Bates, S. H.; Miley, J. W. “Polyol-Bound Colorants Solve    Polyurethane Color Problems”; Proceedings Of The SPI-30th Annual    Technical/Marketing Conference; Technomic: Lancaster, Pa., 1986;    160-165-   Vielee, R. C.; Haney, T. V. “Polyurethanes”; In Coloring of    Plastics; Webber, T. G., Ed., Wiley-Interscience: New York, 1979,    191-204.

UV Stabilizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable UV stabilizers. Polyurethanes based onaromatic isocyanates will typically turn dark shades of yellow uponaging with exposure to light. A review of polyurethane weatheringphenomena is presented in: Davis, A.; Sims, D. Weathering Of Polymers;Applied Science: London, 1983, 222-237. The yellowing is not a problemfor most foam applications. Light protection agents, such ashydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiarybutylcatechol, hydroxybenzophenones, hindered amines and phosphites havebeen used to improve the light stability of polyurethanes. Colorpigments have also been used successfully.

Flame Retardants

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable flame retardants. Low-density, open-celledflexible polyurethane foams have a large surface area and highpermeability to air and thus will burn given the application ofsufficient ignition source and oxygen. Flame retardants are often addedto reduce this flammability. The choice of flame retardant for anyspecific foam often depends upon the intended service application ofthat foam and the attendant flammability testing scenario governing thatapplication. Aspects of flammability that may be influenced by additivesinclude the initial ignitability, burning rate and smoke evolution.

The most widely used flame retardants are the chlorinated phosphateesters, chlorinated paraffins and melamine powders. These and many othercompositions are available from specialty chemical suppliers. A reviewof this subject has been given: Kuryla, W. C.; Papa, A. J. FlameRetardancy of Polymeric Materials, Vol. 3; Marcel Dekker: New York,1975, 1-133.

Bacteriostats

Under certain conditions of warmth and high humidity, polyurethane foamsare susceptible to attack by microorganisms. When this is a concern,additives against bacteria, yeast or fungi are added to the foam duringmanufacture. In certain embodiments, B-side mixtures of the presentinvention comprise one or more suitable bacteriostats.

Plasticizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable plasticizers. Nonreactive liquids havebeen used to soften a foam or to reduce viscosity for improvedprocessing. The softening effect can be compensated for by using apolyol of lower equivalent weight, so that a higher cross-linked polymerstructure is obtained. These materials increase foam density and oftenadversely affect physical properties.

Cell-Openers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable cell openers. In some polyurethane foamsit is necessary to add cell-openers to obtain foam that does not shrinkupon cooling. Known additives for inducing cell-opening includesilicone-based antifoamers, waxes, finely divided solids, liquidperfluocarbons, paraffin oils, long-chain fatty acids and certainpolyether polyols made using high concentrations of ethylene oxide.

Antistatic Agents

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable antistatic compounds. Some flexible foamsare used in packaging, clothing and other applications where it isdesired to minimize the electrical resistance of the foam so thatbuildup of static electrical charges is minimized. This hastraditionally been accomplished through the addition of ionizable metalsalts, carboxylic acid salts, phosphate esters and mixtures thereof.These agents function either by being inherently conductive or byabsorbing moisture from the air. The desired net result is orders ofmagnitude reduction in foam surface resistivity.

Compatibilizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable compatibilizers. Compatibilizers aremolecules that allow two or more nonmiscible ingredients to cometogether and give a homogeneous liquid phase. Many such molecules areknown to the polyurethane industry, these include: amides, amines,hydrocarbon oils, phthalates, polybutyleneglycols, and ureas.

Certain Embodiments

In certain embodiments, the present invention can be described as in thefollowing clauses.

-   1. A method for increasing the load bearing properties of a    polyurethane foam composition, the foam composition comprising the    reaction product of a polyol component and a polyisocyanate    component, the method comprising the step of incorporating into the    polyol component a polycarbonate polyol derived from the    copolymerization of one or more epoxides and carbon dioxide, wherein    the polycarbonate polyol is added in a quantity from about 2 weight    percent to about 50 weight percent of all polyols present in the    polyol component.-   2. The method of clause 1, wherein the polyol component comprises    one or more polyols selected from the group consisting of polyether    polyols, polyester polyols, aliphatic polyols, and mixtures of any    two or more of these.-   3. The method of clause 1, wherein the polyol component    substantially comprises polyether polyol.-   4. The method of clause 1, wherein the polycarbonate polyol is added    in a quantity from about 5 weight percent, to about 25 weight    percent of all polyol present in the polyol component.-   5. The method of clause 4, wherein the polycarbonate polyol is added    in a quantity from about 2 weight percent to about 10 weight percent    of all polyol present in the polyol component.-   6. The method of clause 4, wherein the polycarbonate polyol is added    in a quantity from about 10 weight percent, to about 20 weight    percent of all polyol present in the polyol component.-   7. The method of clause 4, wherein the polycarbonate polyol is added    in a quantity from about 20 weight percent, to about 30 weight    percent of all polyol present in the polyol component.-   8. The method of clause 4, wherein the polycarbonate polyol is added    in a quantity from about 30 weight percent, to about 50 weight    percent of all polyol present in the polyol component.-   9. The method of clause 1, wherein a compression force deflection    (CFD) value measured according to ASTM D3574 of the foam composition    comprising the added polycarbonate polyol is greater than the CFD    value of the corresponding foam composition lacking the added    polycarbonate polyol.-   10. The method of clause 9, wherein the CFD value of the foam    composition comprising the added polycarbonate polyol is at least    10%, at least 20%, at least 30%, at least 40% or at least 50%    greater than the CFD value of the corresponding foam composition    lacking the added polycarbonate polyol.-   11. The method of clause 10, wherein the CFD value of the foam    comprising the added polycarbonate polyol is at least 20%, at least    30%, at least 40% or at least 50% greater than the CFD value of the    corresponding foam without the added polycarbonate polyol.-   12. The method of any one of clauses 9-11, wherein the CFD values    are normalized for density of the foam compositions being compared.-   13. The method of any one of clauses 9-11, wherein the foam    compositions are formulated such that the foam composition    comprising the added polycarbonate polyol and the corresponding foam    composition lacking the added polycarbonate polyol have    substantially the same density.-   14. The method of clause 1, wherein the foam composition comprises    flexible polyurethane foam.-   15. The method of clause 1, wherein the foam composition comprises    viscoelastic polyurethane foam.-   16. The method of clause 1, wherein the foam composition comprises    rigid polyurethane foam.-   17. The method of clause 1, wherein the density measured according    to ASTM D3574 of the foam composition comprising the added    polycarbonate polyol is less than the density of the corresponding    foam composition lacking the added polycarbonate polyol, and wherein    a compression force deflection (CFD) value measured according to    ASTM D3574 of the foam composition comprising the added    polycarbonate polyol is greater than the CFD value of the    corresponding foam composition lacking the added polycarbonate    polyol.-   18. The method of clause 18, wherein the density of the foam    composition comprising the added polycarbonate polyol is at least    10% less than the density of the corresponding foam composition    lacking the added polycarbonate polyol.-   19. The method of clause 18, wherein the density of the foam with    the added polycarbonate polyol is at least 20% less than the density    of the corresponding foam without the added polycarbonate polyol.-   20. The method of clause 19, wherein the density of the foam with    the added polycarbonate polyol is at least 25%, at least 30%, at    least 40% or at least 50% greater than the CFD value of the    corresponding foam without the added polycarbonate polyol.-   21. The method of any of clauses 17-19, wherein the CFD value of the    foam composition comprising the added polycarbonate polyol is at    least 10% greater than the CFD value of the corresponding foam    composition lacking the added polycarbonate polyol.-   22. The method of clause 21, wherein the CFD value of the foam    comprising the added polycarbonate polyol is at least 20%, at least    30%, at least 40% or at least 50% greater than the CFD value of the    corresponding foam without the added polycarbonate polyol.-   23. The method of clause 1, wherein the polycarbonate polyol    contains a primary repeating unit having a structure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

-   24. The method of clause 23, wherein the polycarbonate polyol    contains a primary repeating unit having a structure:

-   25. The method of clause 24, wherein R¹ is, at each occurrence in    the polymer chain, independently —H, or —CH₃.-   26. The method of clause 25, wherein the polycarbonate polyol is    characterized in that it has an Mn between about 500 g/mol and about    20,000 g/mol.-   27. The method of clause 26, wherein the polycarbonate polyol is    characterized in that it has an Mn between about 1,000 g/mol and    about 5,000 g/mol.-   28. The method of clause 26, wherein the polycarbonate polyol is    characterized in that it has an Mn between about 1,000 g/mol and    about 3,000 g/mol.-   29. The method of clause 28, wherein the polycarbonate polyol is    characterized in that it has an Mn of about 1,000 g/mol, about 1,200    g/mol, about 1,500 g/mol, about 2,000 g/mol, about 2,500 g/mol or    about 3,000 g/mol.-   30. The method of clause 25, wherein the aliphatic polycarbonate    polyol is characterized in that more than 98%, more than 99%, or    more than 99.5% of the chain ends are groups reactive toward    isocyanate.-   31. The method of clause 25, wherein the chain ends reactive toward    isocyanate comprise —OH groups.-   32. A polyurethane foam composition comprising the reaction product    of a polyol component and a polyisocyanate component, wherein the    polyol component comprises a polycarbonate polyol derived from the    copolymerization of one or more epoxides and carbon dioxide, wherein    the polycarbonate polyol is present in a quantity from about 2    weight percent to about 50 weight percent of all polyols present in    the polyol component and characterized in that a compression force    deflection (CFD) value measured according to ASTM D3574 of the foam    composition comprising the added polycarbonate polyol is greater    than the CFD value of a corresponding foam composition lacking the    polycarbonate polyol.-   33. The polyurethane foam composition of clause 32, wherein the    polyol component comprises one or more polyols selected from the    group consisting of polyether polyols, polyester polyols, aliphatic    polyols, and mixtures of any two or more of these.-   34. The polyurethane foam composition of clause 32, wherein the    polyol component substantially comprises polyether polyol.-   35. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol is present in a quantity from about 5 weight    percent, to about 25 weight percent of all polyol present in the    polyol component.-   36. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol is present in a quantity from about 2 weight    percent to about 10 weight percent of all polyol present in the    polyol component.-   37. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol is present in a quantity from about 10 weight    percent, to about 20 weight percent of all polyol present in the    polyol component.-   38. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol is present in a quantity from about 20 weight    percent, to about 30 weight percent of all polyol present in the    polyol component.-   39. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol is present in a quantity from about 30 weight    percent, to about 50 weight percent of all polyol present in the    polyol component.-   40. The polyurethane foam composition of clause 32, wherein the CFD    value of the foam composition comprising the polycarbonate polyol is    at least 10% greater than the CFD value of the corresponding foam    composition lacking the polycarbonate polyol.-   41. The polyurethane foam composition of clause 40, wherein the CFD    value of the foam with the polycarbonate polyol is at least 20%, at    least 30%, at least 40% or at least 50% greater than the CFD value    of the corresponding foam without the polycarbonate polyol.-   42. The polyurethane foam composition of clause 40 or 41, wherein    the CFD values are normalized for density of the foam compositions    being compared.-   43. The polyurethane foam composition of clause 40 or 41, wherein    the foam composition is formulated such that the foam composition    comprising the added polycarbonate polyol and the corresponding foam    composition lacking the added polycarbonate polyol have    substantially the same density.-   44. The polyurethane foam composition of clause 32, wherein the foam    composition comprises flexible polyurethane foam.-   45. The polyurethane foam composition of clause 32, wherein the foam    composition comprises viscoelastic polyurethane foam.-   46. The polyurethane foam composition of clause 32, wherein the foam    composition comprises rigid polyurethane foam.-   47. The polyurethane foam composition of clause 32, wherein the    density measured according to ASTM D3574 of the foam composition    comprising the polycarbonate polyol is less than the density of the    corresponding foam composition lacking the polycarbonate polyol.-   48. The polyurethane foam composition of clause 47, wherein the    density of the foam comprising the polycarbonate polyol is at least    10% less than the density of the corresponding foam composition    lacking the added polycarbonate polyol.-   49. The polyurethane foam composition of clause 47, wherein the    density of the foam with the added polycarbonate polyol is at least    20%, at least 30%, at least 40% or at least 50% greater than the CFD    value of the corresponding foam composition without the added    polycarbonate polyol.-   50. The polyurethane foam composition of any of clauses 47-49,    wherein the measured CFD value is at least 10% greater than the CFD    value of the corresponding foam composition lacking the    polycarbonate polyol.-   51. The polyurethane foam composition of clause 50, wherein the CFD    value of the foam with the polycarbonate polyol is at least 20%, at    least 30%, at least 40% or at least 50% greater than the CFD value    of the corresponding foam without the added polycarbonate polyol.-   52. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol contains a primary repeating unit having a    structure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

-   53. The polyurethane foam composition of clause 32, wherein the    polycarbonate polyol contains a primary repeating unit having a    structure:

-   54. The polyurethane foam composition of clause 32, wherein R¹ is,    at each occurrence in the polymer chain, independently —H, or —CH₃.-   55. The polyurethane foam composition of clause 54, wherein the    polycarbonate polyol is characterized in that it has an Mn between    about 500 g/mol and about 20,000 g/mol.-   56. The polyurethane foam composition of clause 55, wherein the    polycarbonate polyol is characterized in that it has an Mn between    about 1,000 g/mol and about 5,000 g/mol.-   57. The polyurethane foam composition of clause 55, wherein the    polycarbonate polyol is characterized in that it has an Mn between    about 1,000 g/mol and about 3,000 g/mol.-   58. The polyurethane foam composition of clause 55, wherein the    polycarbonate polyol is characterized in that it has an Mn of about    1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000    g/mol, about 2,500 g/mol or about 3,000 g/mol.-   59. The polyurethane foam composition of clause 55, wherein the    polycarbonate polyol is characterized in that more than 98%, more    than 99%, or more than 99.5% of the chain ends are groups reactive    toward isocyanate.-   60. The polyurethane foam composition of clause 59, wherein the    chain ends reactive toward isocyanate comprise —OH groups.-   61. A seating foam comprising the reaction product between an    isocyanate component and a polyol component wherein the polyol    component comprises from about 5 weight percent to about 20 weight    percent of a polycarbonate polyol having a primary repeating unit    with the structure:

wherein,

-   -   R¹ is, at each occurrence in the polymer chain, independently        —H, or —CH₃;    -   the polycarbonate polyol has an Mn between about 1,000 g/mol and        about 5,000 g/mol; and    -   the polycarbonate polyol is characterized in that more than 99%        of the chain ends are groups reactive toward isocyanate.

-   62. A viscoelastic foam article comprising the reaction product    between an isocyanate component and a polyol component wherein the    polyol component comprises from about 5 weight percent to about 20    weight percent of a polycarbonate polyol having a primary repeating    unit with the structure:

wherein,

-   -   R¹ is, at each occurrence in the polymer chain, independently        —H, or —CH₃;    -   the polycarbonate polyol has an Mn between about 1,000 g/mol and        about 5,000 g/mol; and    -   the polycarbonate polyol is characterized in that more than 99%        of the chain ends are groups reactive toward isocyanate.

What is claimed is:
 1. A method for increasing the strength of apolyurethane foam composition, the foam composition comprising thereaction product of a polyol component and a polyisocyanate component,the method comprising the step of incorporating into the polyolcomponent a polycarbonate polyol derived from the copolymerization ofone or more epoxides and carbon dioxide, wherein the polycarbonatepolyol is added in a quantity from about 2 weight percent to about 50weight percent, from about 5 weight percent to about 25 weight percent,from about 2 weight percent to about 10 weight percent, from about 10weight percent to about 20 weight percent, from about 20 weight percentto about 30 weight percent, or from about 30 weight percent to about 50weight percent of all polyols present in the polyol component; wherein atear strength value measured by ASTM D 3574-08 of the foam compositioncomprising the added polycarbonate polyol is greater than the tearstrength value of a corresponding foam composition formulated withoutthe added polycarbonate polyol.
 2. The method of claim 1, wherein thepolyol component comprises one or more polyols selected from the groupconsisting of polyether polyols, polyester polyols, aliphatic polyols,and mixtures of any two or more of these.
 3. The method of claim 2,wherein the polyol component comprises polyether polyol.
 4. The methodof claim 1, wherein the tear strength value of the foam compositioncomprising the added polycarbonate polyol is at least 10%, at least 20%,at least 30%, at least 40%, at least 50%, or at least 100% greater thanthe tear strength value of the corresponding foam composition formulatedwithout the added polycarbonate polyol.
 5. The method of claim 1,wherein the tear strength values are normalized for density of the foamcompositions being compared.
 6. The method of claim 1, wherein the foamcompositions are formulated such that the foam composition comprisingthe added polycarbonate polyol and the corresponding foam compositionformulated without the added polycarbonate polyol have the same density.7. The method of claim 1, wherein the foam composition comprisesflexible polyurethane foam, or wherein the foam composition comprisesviscoelastic polyurethane foam, or wherein the foam compositioncomprises rigid polyurethane foam.
 8. The method of claim 1, wherein thedensity measured according to ASTM D3574 of the foam compositioncomprising the added polycarbonate polyol is less than the density ofthe corresponding foam composition formulated without the addedpolycarbonate polyol, and wherein the tear strength value measuredaccording to ASTM D3574-08 of the foam composition comprising the addedpolycarbonate polyol is greater than the tear strength value of thecorresponding foam composition formulated without the addedpolycarbonate polyol.
 9. The method of claim 8, wherein the density ofthe foam composition comprising the added polycarbonate polyol is atleast 10%, at least 20%, at least 30%, at least 40% or at least 50% lessthan the density of the corresponding foam composition formulatedwithout the added polycarbonate polyol.
 10. The method of claim 8,wherein the tear strength value of the foam composition comprising theadded polycarbonate polyol is at least 10%, at least 20%, at least 30%,at least 40% or at least 50% greater than the tear strength value of thecorresponding foam composition formulated without the addedpolycarbonate polyol.
 11. The method of claim 1, wherein thepolycarbonate polyol contains a primary repeating unit having astructure:

where R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain,independently selected from the group consisting of —H, fluorine, anoptionally substituted C₁₋₄₀ aliphatic group, an optionally substitutedC₁₋₂₀ heteroaliphatic group, and an optionally substituted aryl group,where any two or more of R¹, R², R³, and R⁴ may optionally be takentogether with intervening atoms to form one or more optionallysubstituted rings optionally containing one or more heteroatoms.
 12. Themethod of claim 11, wherein the polycarbonate polyol contains a primaryrepeating unit having a structure:


13. The method of claim 12, wherein R¹ is, at each occurrence in thepolymer chain, independently —H, or —CH₃.
 14. The method of claim 11,wherein the polycarbonate polyol is characterized in that it has an Mnbetween about 500 g/mol and about 20,000 g/mol, between about 1,000g/mol and about 5,000 g/mol, between about 1,000 g/mol and about 3,000g/mol, or between about 1,000 g/mol and about 3,000 g/mol, or an Mn ofabout 1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000g/mol, about 2,500 g/mol or about 3,000 g/mol.
 15. The method of claim11, wherein the aliphatic polycarbonate polyol is characterized in thatmore than 98%, more than 99%, or more than 99.5% of the chain ends aregroups reactive toward isocyanate.
 16. The method of claim 15, whereinthe chain ends reactive toward isocyanate comprise —OH groups.
 17. Apolyurethane foam composition comprising the reaction product of apolyol component and a polyisocyanate component, wherein the polyolcomponent comprises a polycarbonate polyol derived from thecopolymerization of one or more epoxides and carbon dioxide, wherein thepolycarbonate polyol is present in a quantity from about 2 weightpercent to about 50 weight percent, from about 5 weight percent to about25 weight percent, from about 2 weight percent to about 10 weightpercent, from about 10 weight percent to about 20 weight percent, fromabout 20 weight percent to about 30 weight percent, or from about 30weight percent to about 50 weight percent of all polyols present in thepolyol component and characterized in that a tear strength valuemeasured according to ASTM D 3574-08 of the foam composition comprisingthe added polycarbonate polyol is greater than the tear strength valueof a corresponding foam composition formulated without the addedpolycarbonate polyol.
 18. The polyurethane foam composition of claim 17,wherein the polyol component comprises one or more polyols selected fromthe group consisting of polyether polyols, polyester polyols, aliphaticpolyols, and mixtures of any two or more of these.
 19. The polyurethanefoam composition of claim 18, wherein the polyol component comprisespolyether polyol.
 20. The polyurethane foam composition of claim 17,wherein the tear strength value of the foam composition comprising thepolycarbonate polyol is at least 10%, at least 20%, at least 30%, atleast 40%, at least 50%, or at least 100% greater than the tear strengthvalue of the corresponding foam composition formulated without the addedpolycarbonate polyol.
 21. The polyurethane foam composition of claim 20,wherein the tear strength values are normalized for density of the foamcompositions being compared.
 22. The polyurethane foam composition ofclaim 20, wherein the foam composition is formulated such that the foamcomposition comprising the added polycarbonate polyol and thecorresponding foam composition formulated without the addedpolycarbonate polyol have the same density.
 23. The polyurethane foamcomposition of claim 17, wherein the foam composition comprises flexiblepolyurethane foam or wherein the foam composition comprises viscoelasticpolyurethane foam, or wherein the foam composition comprises rigidpolyurethane foam.
 24. The polyurethane foam composition of claim 17,wherein the density measured according to ASTM D3574-08 of the foamcomposition comprising the polycarbonate polyol is less than the densityof the corresponding foam composition formulated without thepolycarbonate polyol.
 25. The polyurethane foam composition of claim 24,wherein the density of the foam comprising the polycarbonate polyol isat least 10%, at least 20%, at least 30%, at least 40% or at least 50%less than the density of the corresponding foam composition formulatedwithout the added polycarbonate polyol.
 26. The polyurethane foamcomposition of claim 24, wherein the measured tear strength value is atleast 10%, at least 20%, at least 30%, at least 40% or at least 50%greater than the tear strength value of the corresponding foamcomposition formulated without the polycarbonate polyol.
 27. Thepolyurethane foam composition of claim 17, wherein the polycarbonatepolyol contains a primary repeating unit having a structure:

where R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain,independently selected from the group consisting of —H, fluorine, anoptionally substituted C₁₋₄₀ aliphatic group, an optionally substitutedC₁₋₂₀ heteroaliphatic group, and an optionally substituted aryl group,where any two or more of R¹, R², R³, and R⁴ may optionally be takentogether with intervening atoms to form one or more optionallysubstituted rings optionally containing one or more heteroatoms.
 28. Thepolyurethane foam composition of claim 27, wherein the polycarbonatepolyol contains a primary repeating unit having a structure:


29. The polyurethane foam composition of claim 28, wherein R¹ is, ateach occurrence in the polymer chain, independently —H, or —CH₃.
 30. Thepolyurethane foam composition of claim 27, wherein the polycarbonatepolyol is characterized in that it has an Mn between about 500 g/mol andabout 20,000 g/mol, between about 1,000 g/mol and about 5,000 g/mol, orbetween about 1,000 g/mol and about 3,000 g/mol, or an Mn of about 1,000g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000 g/mol, about2,500 g/mol or about 3,000 g/mol.
 31. The polyurethane foam compositionof claim 30, wherein the polycarbonate polyol is characterized in thatmore than 98%, more than 99%, or more than 99.5% of the chain ends aregroups reactive toward isocyanate.
 32. The polyurethane foam compositionof claim 31, wherein the chain ends reactive toward isocyanate compriseOH groups.
 33. The method of claim 1, wherein the polycarbonate polyolis characterized in that, on average in the composition, the percentageof carbonate linkages is 85% or greater.
 34. The method of claim 33,wherein the polycarbonate polyol is characterized in that, on average inthe composition, the percentage of carbonate linkages is 90% or greater.35. The method of claim 34, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 95% or greater.
 36. The method of claim 35,wherein the polycarbonate polyol is characterized in that, on average inthe composition, the percentage of carbonate linkages is 98% or greater.37. The method of claim 36, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 99% or greater.
 38. The polyurethane foamcomposition of claim 17, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 85% or greater.
 39. The polyurethane foamcomposition of claim 38, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 90% or greater.
 40. The polyurethane foamcomposition of claim 39, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 95% or greater.
 41. The polyurethane foamcomposition of claim 40, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 98% or greater.
 42. The polyurethane foamcomposition of claim 41, wherein the polycarbonate polyol ischaracterized in that, on average in the composition, the percentage ofcarbonate linkages is 99% or greater.